KR20100106484A - Heavy oil upgrade process including recovery of spent catalyst - Google Patents

Abstract

A process for improving heavy oils and converting heavy oils to low boiling hydrocarbon products is provided. The process utilizes a catalyst slurry comprising catalyst particles having an average particle size in the range of 1-20 microns. In the refinement process, the spent slurry catalyst in the heavy oil is produced as discharge stream. In one aspect, the process further includes recovering the used catalyst by separating heavy oil from the catalyst particles in the slurry. In one embodiment, the slurry catalyst in heavy oil combines with the solvent to form a combined slurry-solvent stream. The combined slurry-solvent stream is filtered in the deoiling zone using membrane filtration. The hydrocarbons, ie the solvent and residual heavy oil, may then be separated from the catalyst particles in the drying zone. The precious metal may be recovered from the catalyst particles for later reuse in the catalyst synthesis unit, producing a new slurry catalyst.

Description

Heavy Oil Upgrade Process Including Recovery of Spent Catalyst

The stockpile of light oils is becoming increasingly depleted, and the cost of developing heavy oil resources (eg, lifting, mining and extraction) is reduced, necessitating the development of new improvements to convert heavy oils and bitumens into lighter products. This was raised. With the emergence of heavier crude feedstocks, more catalyst must be used in refining than before to improve heavy oils and to remove contaminants / sulfur from these feedstocks. This catalytic process generates a large amount of used catalyst. Due to the increased demand for precious metals and the market price and its environmental awareness, the catalyst can serve as a secondary source for metal recovery.

In order to recycle / recover catalyst metals to provide a renewable source of metals, efforts have been made to extract metals from spent catalysts resulting from heavy oil refinery processes, in the form of supported or bulk catalysts. Before the catalytic metal can be extracted / recovered from the used catalyst, the residual heavy oil obtained from the hydroprocessing operation must first be separated from the used catalyst. The exit stream from the heavy oil refinery system generally comprises unconverted heavy oil material, heavier hydrocracked liquid product, 3 to 50 wt% slurry catalyst, small amounts of coke, asphaltenes and the like. Conventional filtration processes may not be suitable for separating / recovering slurry catalyst from high molecular weight hydrocarbon materials in the effluent stream, as non-supported fine catalyst may clog or contaminate the filter.

Using microfiltration, ultrafiltration, nanofiltration and reverse osmosis, in particular, membrane technology has long been used for the removal of contaminants in environmental purification, wastewater treatment and water purification. (Ppm amount) vanadium is obtained from a low boiling hydrocarbon mixture such as kerosene.

Heavy oils exposed to hydrocracking conditions are particularly difficult to extract / remove / separate from slurry catalysts. Conventional solvent extraction and roasting methods in the prior art are not particularly effective for slurry catalysts, leaving heavy oil in the catalyst particles causing problems in the bottom metal recovery process (recovering precious metals from used catalysts). Some of the chemicals in the residual entrained oils in the catalyst particles cause foaming problems during the metal recovery process, and efforts to recover the metal using chemical extraction, pressure leaching, metal dissolution / solubilization, crystallization and / or precipitation methods, etc. Negatively affects.

It is an object of the present invention to provide a novel use of membrane technology in the separation and / or extraction of residual heavy oil from spent catalyst particles resulting from heavy oil improvement operations.

In one aspect, an integrated system for heavy oil improvement is provided, which system recovers precious metals from a heavy oil improvement unit, a catalyst deoiling unit for separating slurry catalyst used for unconverted heavy oil, and deoiled used slurry catalyst. Metal recovery unit, and a catalyst synthesis unit for forming a slurry catalyst from the recovered metal.

In another aspect, a system for separating heavy oil from catalyst particles is provided. The system utilizes a filtration assembly having a membrane having a pore size sufficient to remove at least 90% of the heavy oil from the catalyst particles. In one embodiment, the filtration assembly comprises a plurality of filtration units selected from cross-flow filtration, diafiltration, dynamic filtration, cross-flow sedimentation, cocurrent sedimentation separation, countercurrent sedimentation separation, and settling tank.

In a third aspect, there is also provided a method of separating fine catalyst from heavy oil using dynamic filtration. The method includes vibrating dynamic filtration of the fine catalyst mixture in heavy oil at a shear force of at least about 20,000 / second.

In a fourth aspect, a method of separating fine catalyst from heavy oil using filtration sedimentation is provided. The method utilizes a sedimentation separator with a module having a plurality of membranes in the form of channels, the channels tilted downward to facilitate the separation of heavy oil from the catalyst.

In a fifth aspect, a system for separating heavy oil from catalyst particles having a drying zone comprising at least two drying steps and having a second drying step for volatilization of organics, such as solvent and heavy oil, from the catalyst particles Is provided. In one embodiment, the first drying zone is a combined horizontal and vertical wiped film dryer / evaporator (or a combined horizontal and vertical thin film dryer / evaporator) and the second zone is a rotary kiln dryer.

In another aspect, a system is provided for separating hydrocarbons from catalyst particles using at least surfactants to remove / clean organics, including solvents and heavy oils, from the catalyst particles.

According to the present invention, membrane technology is used to effectively separate and / or extract residual heavy oil from spent catalyst particles resulting from heavy oil improvement operations.

1A is a cross-sectional view of the plate and frame filtration unit.
1B is a partially exploded view showing an embodiment of a membrane filtration system having a pleated membrane structure.
1C is a schematic of a membrane filtration system with a tubular membrane filter.
1D is a perspective view of a membrane system having a plurality of tubular / hollow membrane filters.
1E is a perspective view of a helical membrane system.
FIG. 2 is a schematic diagram of a countercurrent sedimentation separator having two parallel (backflow) inlet streams into a membrane channel and a receiving chamber arranged in parallel.
FIG. 3 is a schematic of a cross-flow sedimentation separator having membrane channels arranged in parallel and an inlet stream on one side of the channel and an outlet (filtrate) stream on opposite sides of the channel.
4 is a block diagram showing an embodiment of a deoiling operation.
5 is a block diagram of another embodiment of a deoiling unit having a concentration zone.
6 is a block diagram showing a third embodiment of a deoiling unit having a slurry concentration zone.
FIG. 7 is a block diagram showing another embodiment of a deoiling unit, using a concentration zone as well as a slurry concentration zone.
8 is a block diagram illustrating an embodiment of a membrane filtration system having multiple cross-flow filtration units.
9 is a block diagram illustrating an embodiment of a membrane filtration system having a precipitation tank for solvent washing.
10 is a block diagram illustrating an embodiment of a deoiling system having a membrane filtration zone and a two stage drying zone, including a combi dryer and a rotary kiln dryer.
FIG. 11 is a block diagram showing recycling operations in an embodiment using dynamic filtration, such as shear enhanced vibration membrane filtration (V * SEP) units.
12 is a diagram of membrane testing in an embodiment using dynamic filtration, eg, a V * SEP unit.
FIG. 13 is a diagram of a pressure test in an embodiment using dynamic filtration, eg, a V * SEP unit.
14 is a block diagram showing batch operation with dynamic filtration, eg, V * SEP unit.
FIG. 15 is a diagram of a diafiltration test in an embodiment using dynamic filtration, eg, a V * SEP unit.
FIG. 16 is a diagram of particle size distribution in an embodiment using dynamic filtration, eg, a V * SEP unit. FIG.

The following terms will be used throughout this specification and shall have the following meanings unless otherwise indicated.

"Average flow rate" refers to a time weighted average flow rate measured over a certain concentration range.

"Batch concentration" refers to a dynamic filtration system, such as a shear force enhanced vibrating membrane filtration (V * SEP) machine arrangement, in which a fixed amount of feed slurry is gradually concentrated by removal of permeate from the system. The concentrate from the system is returned to the feed tank.

"Concentrate", also known as "retentate", refers to a portion of a slurry that has not permeated through a filter medium, such as a membrane. In other words, this is the portion of the slurry that is not filtered through the membrane.

"Concentration factor" refers to the ratio of feed flow rate to concentrate flow rate.

"Cross-flow" filtration (or crossflow filtration or tangential flow filtration) refers to a filtration technique in which the feed stream flows (parallel or tangentially) along the membrane surface, and the filtrate flows across the membrane. . In cross-flow filtration, when the permeate or filtrate and everything else is retained on the feed side of the membrane as retentate or concentrate, generally only material that is smaller than the membrane pore size passes through (cross). In one embodiment of cross-flow filtration, only the liquid portion in the solid containing stream passes through the filter medium, ie the membrane. On the other hand, in conventional filtration (dead-end or normal filtration), rather than just a portion of the liquid, the entire liquid portion of the slurry is retained by the membrane with most or all solids retained. Will pass.

"Diafiltration (DF)" refers to a cross-flow filtration process in which a buffer material, such as a solvent, is added to the feed stream and / or the filtration process while the filtrate is continuously removed from the process. In one embodiment of diafiltration, the process is used to purify retained high molecular weight species, increase the recovery of low molecular weight species, buffer exchange and simply change the properties of a given solution. Diafiltration may be in the form of batch diafiltration or continuous diafiltration. In batch diafiltration, the retentate is concentrated to the original volume or to a certain concentration of slurry catalyst in the retentate. Once this concentration is reached, another volume of feed stream is added. In continuous diafiltration, the volume of the feed stream (catalyst slurry in solvent and heavy oil) is added to the filtration process at the same rate as the filtrate and concentrate are removed. By this method, the liquid volume in the process can be kept constant even while smaller molecules that can permeate the filter, such as heavy oil in the solvent, are washed off in the filtrate.

“Dynamic filtration” is an extension of cross-flow filtration that pushes particulate matter out of the filter element and disrupts the formation of cake layers adjacent to the filter medium, thereby essentially freeing or contaminating the filter medium. This result is achieved by moving and filtering the material against the filter medium fast enough to produce high lift forces and high shear rates on the particles, such as the use of rotation, oscillating, reciprocating, or vibrating means. Is achieved. Tangential or crossover (which presents other problems such as premature filter plugging due to compound adsorption and a significant non-uniform pressure drop associated with high tangential velocity along the filter length, potentially causing backflow through the filtration medium and reducing filtration) Unlike the flow filtration technique, the shear at the liquid-filter media interface is almost independent of any cross flow liquid velocity.

"Microfiltration" refers to a membrane filtration process in which hydrostatic pressure is applied to a liquid with respect to the membrane using a microporous membrane, ie, a membrane having a pore size in the micron range. Microfiltration can be in the form of cross-flow filtration, diafiltration, or dynamic filtration. In one embodiment, the film size is less than 100 nm. In another embodiment, the film size ranges from 0.01 to 10 microns (10 to 10,000 nm). In one embodiment, membranes of sufficient size are used to retain particles of size or weight of 0.1 μm or 500,000 daltons or more.

"Nanofiltration" refers to low to moderately high pressures (typically> 4 bar) using filters with very small pore sizes, ie nanofilters with membranes with pore sizes in nanometers (1 nm = 10 μs or 0.001 μm). , Or 50-450 psig).

"Feed" may be used interchangeably with "feed slurry" and refers to a mixture comprising heavy oil and slurry catalyst used for filtration. The feed is generally a dispersion of solids or molecules, which are separated from the clear filtrate and reduced in size to form a concentrated solution of the feed slurry.

"Pollution" refers to the accumulation of material on the membrane surface or structure, causing a decrease in flow rate.

"Flow" refers to a measure of the volume of liquid passing through the membrane over a certain time interval relative to the set area of the membrane (i.e., gallons per liter (gfd) or L / m ² per hour produced in ft ² of membrane per day).

"Instantaneous flow rate" refers to the flow rate measured at a given moment in time.

"Line-out test" refers to the process of measuring the membrane flow rate over time to determine the final stability.

"Optimal differential pressure" refers to a differential pressure value at which the rate of flow rate change over time or the filtration productivity decreases further.

"Recovery ratio" refers to the ratio of permeate flow rate to feed flow rate.

"Permeate", also known as "filtrate", refers to the portion of slurry that has permeated through a membrane. The amount of solids contained in the filtrate and the particle size of the solids are determined by the pore size of the fractionating membrane, among other factors.

"Surfactant" or "surfactant" refers to any compound that reduces surface tension when dissolved or dispersed in water or aqueous solution, or reduces the interfacial tension between two liquids or between a liquid and a solid. In related aspects, there are three or more categories of surface agents: detergents, wetting agents and emulsifiers; All of these use the same basic chemical mechanism and differ, for example, in the nature of the surfaces involved.

"Detergent" refers to an emulsifier or surface agent generally formed by the action of an alkali on fat or fatty acids, such as, but not limited to, sodium or potassium salts of fatty acids, or sulfonates formed when sulfonic acids react with alkanes. . In one embodiment, the detergent may include any of a number of synthetic water soluble or liquid organic formulations that are chemically different from soap, but that can emulsify oil to retain dirt in suspension and act as humectant.

"Heavy oil" refers to heavy and ultra-heavy crude oils, including but not limited to residues, coal, bitumen, tar sands, and the like. The heavy oil feedstock may be liquid, semisolid and / or solid. Examples of heavy oil feedstocks that can be improved as described herein include vacuum resids from Canadian tar sands, Brazilian Santos and Campos basins, Egyptian Suezmann, Chad, Venezuela Giulia, Malaysia and Sumatra Indonesia This is not restrictive. Other examples of heavy oil feedstocks include "bottom of the barrel" and "residuum or resid"-tower bottoms having a boiling point of at least 343 ° C (650 ° F), Or a refining tower reservoir having a boiling point of at least 524 ° C. (975 ° F.), or “resid pitch” and “reduced residue” having a boiling point of at least 524 ° C. (975 ° F.). Bottom of the barrel and residue. The characteristics of the heavy oil feedstock include a TAN of at least 0.1, at least 0.3, or at least 1; Viscosity of at least 10 cSt; In one embodiment, at most 20, in another embodiment at most 10, and in another embodiment, may include, but is not limited to, an API specific gravity. 1 g of heavy oil feedstock generally has at least 0.0001 g of Ni / V / Fe per gram of crude oil; At least 0.005 g heteroatoms; At least 0.01 g of residue; At least 0.04 g C5 asphaltenes; At least 0.002 g of MCR; At least 0.00001 g of alkali metal salt of at least one organic acid; And at least 0.005 g of sulfur. In one embodiment, the heavy oil feedstock has a sulfur content of at least 5% by weight and an API specific gravity of -5 to +5. Heavy oil feeds, including Asabasca bitumen (Canada), generally have at least 50% by volume of vacuum residue. The Boskan (Venezuela) heavy oil feed may comprise at least 64% by volume of vacuum residue.

As used herein, the term “catalyst used” refers to a catalyst whose activity is reduced, unchanged or improved by being used in hydroprocessing operations. For example, assuming a reaction rate constant of 100% for a new catalyst at a particular temperature, the reaction rate constant of the catalyst used at that temperature is 80% or less in one embodiment and 50% or less in another embodiment. In one embodiment, the metal component of the spent catalyst comprises at least one of Group VB, Group VIB and Group VIII metals, such as vanadium, molybdenum, tungsten, nickel and cobalt. The most commonly encountered rapid is molybdenum. In one embodiment, the metal of the spent catalyst is a sulfide of Mo, Ni and V.

The terms "treatment", "treated", "improved", "improved" and "improved" when used with heavy oil feedstock, are subjected to a hydrogenation process or have a coarse heavy oil feedstock, or the molecular weight of the heavy oil feedstock Reduced, reduced boiling range of feedstock, reduced concentration of asphaltenes, reduced concentration of hydrocarbon-free radicals, and / or reduced amounts of impurities such as sulfur, nitrogen, oxygen, halides and metals Refers to a substance or crude product.

In one embodiment, the present invention provides a process comprising: 1) a heavy oil improvement process (or zone) in which the heavy oil feed is converted to a lighter product; 2) a deoiling process or zone in which residual heavy oil and heavier product oil are separated from the used slurry catalyst for subsequent recovery; 3) a metal recovery zone where metal is recovered from the catalyst used; And 4) a catalytic synthesis zone for synthesizing the catalyst from a metal obtained from a source comprising a metal recovered from the catalyst used. Any of these regions can be operated in a batch manner, continuous manner or a combination thereof.

In one embodiment of the present invention involving the recovery / separation of the catalyst used from heavy oil, the heavy oil conversion can be up to 100%. In one embodiment, an integrated system having a deoiling zone for recovery / separation of the catalyst used allows heavy oil conversion of up to 99.5%. In another embodiment, the overall heavy oil conversion is up to 99%. As used herein, conversion refers to the conversion of heavy oil feedstock to a material having a boiling point of less than 1000 ° F. (538 ° C.).

Heavy oil improvement

Improvement or treatment of heavy oil feed is generally referred to as a "hydrogenation process". Hydrogenation processes include, but are not limited to, hydrocracking including hydroconversion, hydrocracking, hydrogenation, hydrotreating, hydrodesulfurization, hydrodenitrification, hydrodemetallization, hydrodearomatics, hydroisomerization, hydrodewaxing, and selective hydrocracking. Means any process carried out in the presence of hydrogen. The products of the hydrogenation process can exhibit improved viscosity, viscosity index, saturate content, low temperature properties, volatility and polarization.

Heavy oil improvements include heavy oil or bitumen, which are commercially valuable lighter products, such as, in one embodiment, liquefied petroleum gas (LPG), gasoline, jet, diesel, reduced pressure gas oil (VGO) and fuel oil. It is used to convert to lower boiling hydrocarbons.

In the heavy oil refinement process, the heavy oil feed is treated or improved by contact with the slurry catalyst feed in the presence of hydrogen and converted to a lighter product, a) a mixture of the improved product, slurry catalyst, hydrogen containing gas and crude An output stream comprising a conversion heavy oil feedstock, which is then passed to a separation zone; And b) finely divided non-supported catalysts, carbon fines and metal fines used in unconverted residue hydrocarbon oil and heavier hydrocracked liquid product (collectively “heavy oil”) as slurry catalyst. Create a stream that is defined as a conversion slurry bleeding oil stream (“USBO”). The solids content in the USBO stream may range from about 5-40 wt% in one embodiment, 10-30 wt% in a second embodiment, and about 15-25 wt% in a third embodiment. In one embodiment, the refinement process includes a plurality of reactors or contacting zones where the arrangement of the reactors is the same or different. Examples of reactors that may be used herein include stacked bed reactors, fixed bed reactors, ebullating bed reactors, continuous stirred tank reactors, fluidized bed reactors, spray reactors, liquid / liquid contactors, slurry reactors, slurry bubbles Column reactors, liquid recycle reactors, and combinations thereof.

In one embodiment, the at least one contacting zone further comprises an in-line hydrotreater capable of removing at least 70% of sulfur, at least 90% of nitrogen, and at least 90% of heteroatoms from the treated crude product. In one embodiment, the improved heavy oil feed from the contacting zone is fed directly to the separation zone or, after one or more intermediate processes, directly to a separation zone, such as a flash drum or a high pressure separator, so that gas and volatile liquids are Non-volatile fractions such as unconverted slurry bleeding oil stream ("USBO").

In one embodiment, at least 90% by weight heavy oil feed is converted to lighter product in the refinement system. In a second embodiment, at least 95% of the heavy oil feed is converted to lighter product. In a third embodiment, the conversion rate is at least 98%. In a fourth embodiment, the conversion rate is at least 99.5%. In a fifth embodiment the conversion is at least 80%.

In one embodiment, the heavy oil refinement process utilizes a slurry catalyst. The catalyst slurry can be concentrated prior to heavy oil refinement, for example, to assist in the transport of catalyst (slurry) to the heavy oil refinery site. The discharge stream from the reactor, possibly following a subsequent process such as separation, may comprise one or more valuable light products, as well as a stream comprising slurry / unsupported catalysts used in heavy oil comprising unconverted feed. .

Catalytic synthesis

In one embodiment, the used slurry catalyst to be separated from the heavy oil is a Group VB metal such as V, Nb; Group VIII metals such as Ni and Co; Group VIIIB metals such as Fe; Group IVB metals such as Ti; Derived from a dispersed (bulk or non-supported) Group VIB metal sulfide catalyst, enhanced by at least one of Group IIB metals such as Zn and combinations thereof. Promoters are generally added to catalyst formulations to enhance selected properties of the catalyst or to change catalyst activity and / or selectivity. In another embodiment, the slurry catalyst is derived from a dispersed (bulk or non-supported) Group VIB metal sulfide catalyst enhanced with a Group VIII metal for a hydrocarbon oil hydrogenation process.

In one embodiment, the slurry catalyst is derived from a multi-metal catalyst comprising at least a Group VIB metal and optionally (as a promoter) at least a Group VIII metal, which metals may be in atomic form or in the form of metal compounds. The metal used to prepare the catalyst may be metal recovered from the bottom metal recovery unit, and metals such as molybdenum, nickel and the like are recovered from the deoiled slurry catalyst for use in the synthesis of fresh / new slurry catalysts.

In one embodiment, the slurry catalyst is derived from a catalyst made from a mononuclear, binuclear or multinuclear molybdenum oxysulfide dithiocarbamate complex. In a second embodiment the catalyst is prepared from molybdenum oxysulfide dithiocarbamate complex. In one embodiment, the slurry catalyst is derived from a catalyst prepared from a catalyst precursor composition comprising an organometallic complex or compound, such as a fat soluble compound or complex of a transition metal and an organic acid. Examples of such compounds are naphthenates, pentanedionates of group VIB and group VII metals such as Mo, Co, W and the like, such as molybdenum naphthenate, vanadium naphthenate, vanadium octanoate, hexacarbonyl molybdenum and hexacarbonyl vanadium , Octanates and acetates.

In one embodiment, the catalyst slurry comprises catalyst particles or particles having an average particle size of at least 1 micron in a hydrocarbon oil diluent. In another embodiment, the catalyst slurry comprises catalyst particles having an average particle size in the range of 1-20 microns. In a third embodiment the catalyst particles have an average particle size in the range of 2-10 microns. In one embodiment, the slurry catalyst comprises a catalyst having an average particle size ranging from colloidal (nanometer size) to about 1-2 microns. In another embodiment, the slurry catalyst comprises a catalyst having extremely small particles of molecular and / or colloidal size (ie, less than 100 nm, less than about 10 nm, less than about 5 nm and less than about 1 nm). Aggregates having an average size of 1 to 10 microns in an embodiment, 1 to 20 microns in another embodiment, and less than 10 microns in a third embodiment.

Deoiling  domain

The system for extracting / recovering / separating heavy oil from the slurry catalyst and / or concentrating the catalyst slurry is called a deoiling zone (unit). In one embodiment of the deoiling zone, the heavy oil is extracted or separated from the catalyst particles to form a clean dry solid for subsequent recovery in the metal recovery zone. In one embodiment, the deoiling zone comprises a plurality of separate sub-units including solvent washing (solvent extraction), filtration, drying and solvent recovery sub-units.

In one embodiment, the deoiling zone is used to concentrate the catalyst slurry, for example to a solids content of about 60-70% by weight. In part, due to the concentrated catalyst slurry having a reduced volume compared to the catalyst slurry volume before concentration, the concentrated catalyst slurry can then be more easily transported to the heavy oil refinery site or to the reactor, where prior to heavy oil improvement, for example , To a solids content of about 5% by weight.

The term “used catalyst slurry” refers to used catalyst slurry that is separated from heavy oil or freshly made catalyst slurry that needs to be concentrated.

The term "extraction" can be used interchangeably with "separation" or "recovery" (or grammatical variants thereof) and means the separation of heavy oil from catalyst particles (or particles).

In one embodiment, the feed stream to the deoiling zone is a catalyst bleeding stream from a heavy oil refinery or reduced pressure residue unit, such as an unconverted slurry bleeding oil ("USBO") stream, containing unconverted residue hydrocarbon oil and heavier In the hydrocracked liquid product (collectively "heavy oil"), the finely divided non-supported catalyst, carbon fines, and metal fines used are included. In one embodiment, the USBO feed stream to the deoiling process has a used catalyst concentration in the range of 5-40% by weight (as a solid). In another embodiment, the catalyst solids used range from 10 to 20 weight percent of the total USBO feed stream. The clean dry solids out of the deoiling process essentially consist of, in one embodiment, the used catalyst solids having less than 1% by weight of oil, based on solvent absence with less than 500 ppm of solvent.

In one embodiment, before being filtered through membrane filtration, the feedstock stream first combines with the solvent to form a combined slurry-solvent stream. In another embodiment the feedstock stream and the solvent are fed to the filter as separate feed streams, which are combined in the filtration process. In one embodiment, fresh solvent is used for solvent washing. In another embodiment, solvent recycled from another part of the process is used. In a third embodiment, a mixture of fresh and recycled solvents is used. In a fourth embodiment, fresh solvent and recycled solvent are used as separate streams. The feedstock and solvent stream may be combined before or in the deoiling zone.

Through membrane filtration, the catalyst used is separated from the heavy oil, ie “deoiled” in the solvent as a separate stream. A second stream is produced comprising heavy oil and a solvent. The solvent may then be separated from the catalyst using a process including evaporation drying. The solvent may be recovered from a stream comprising heavy oil and solvent or for later reuse, and the recovered heavy oil becomes a product.

In one embodiment, in addition to or in place of membrane filtration, other separation techniques, including gradient plate settler, existing settling tanks, and gradient settler with vibration separation mechanism, unless vibrations propagate to the settler / settling unit. This can be used.

Membrane filtration

In one embodiment, a membrane filtration assembly such as fine filtration can be used in the deoiling zone to separate heavy oil from the catalyst. In the filtration assembly, the feed stream comprising the slurry catalyst in heavy oil comprises two streams, essentially a first stream containing a mixture of hydrocarbons such as heavy oil and a solvent and a catalyst solid having a reduced heavy oil concentration in the solvent. Converted to 2 streams. When used in the context of deoiling zone / membrane filtration, "heavy oil" will refer to unconverted residue hydrocarbon oil, heavier hydrocracked liquid products, and mixtures thereof.

The membrane used may be a combination of multiple membrane layers, which is of the "meso-pore" or "capillary-pore" type, or some of which are meso-porous membranes and some of which are capillary-pore membranes. Here, mesoporous-pore refers to a membrane having a structure similar to a sponge with a network that crosses mesopores. Capillary-pore refers to a membrane having a cylindrical capillary tube that passes approximately straight through.

Any suitable filtration medium (membrane) can be used in the filtration assembly. In one embodiment, the filtration medium is a porous material that retains catalyst particles used in the retentate while allowing heavy oil below a certain size to flow through as a filtrate (or permeate). In one embodiment, the filtration medium has a pore size sufficient to remove at least 50% of the heavy oil from the catalyst used, ie at least 50% of the heavy oil passes through the filter membrane. In another embodiment, the filter membrane has a pore size sufficient for at least 60% of heavy oil to pass through the membrane. In a third embodiment, the membrane has a pore size sufficient for at least 70% of heavy oil to pass through the membrane. In a fourth embodiment, the pores are large enough for at least 75% of heavy oil to pass through the membrane.

In one embodiment, as filtration media, filtration membranes having an effective pore rating (“average pore size”) of about 5 microns or less, such as about 0.1-0.3 μm, about 0.05-0.15 μm, or about 0.1 μm, are used. . In a third embodiment, an effective pore rating of about 1 micron or less is used. In a fourth embodiment, an effective pore rating of about 0.5 micron or less is used. In a fifth embodiment, the membrane has an effective pore rating of at least 0.01 micron. In a sixth embodiment, it has an effective pore rating of 0.1 to 1 micron. In a seventh embodiment, it has an effective pore rating of at least 1 micron. In an eighth embodiment it has an effective pore rating of less than 10 microns.

Polymers, organic materials, inorganic ceramic materials, and metals, if solvent-stable, are suitable for use as constituent materials for membranes. The term "solvent-stable" refers to a material that does not undergo significant chemical changes that substantially impair the desired properties of the material. Stability can be confirmed by various known techniques, including but not limited to soaking test, scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis ( TGA).

In one embodiment, the filtration membrane is made of polytetrafluoroethylene (Teflon ^® ), such as polytetrafluoroethylene on woven glass fibers, which can withstand temperatures of 130 ° C. (266 ° F.). With the use of polytetrafluoroethylene, the membrane is chemically inert and can tolerate continuous pH levels of 0-14.

In one embodiment, the filtration membrane is poly (acrylic acid), poly (acrylate), polyacetylene, poly (vinyl acetate), polyacrylonitrile, polyamine, polyamide, polysulfonamide, polyether, polyurethane, polyimide , Polyvinyl alcohol, polyester, cellulose, cellulose ester, cellulose ether, chitosan, chitin, elastomer, halogenated polymer, fluoroelastomer, polyvinyl halide, polyphosphazene, polybenzimidazole, poly (trimethylsilylpropine), Polymeric materials selected from the group of polysiloxanes, poly (dimethyl siloxanes), and copolymer blends thereof. These polymers may be physically or chemically crosslinked to further improve their solvent stability.

In one embodiment, the membrane comprises inorganic materials such as ceramics (silicon carbide, zirconium oxide, titanium oxide, etc.) having the ability to withstand high temperatures and harsh environments. In one embodiment, the membrane consists of a fabric coated with nanomaterials, such as inorganic metal oxides, such that the membrane is in the form of a flexible ceramic membrane foil having the advantages of both ceramic and polymeric membranes. In another embodiment, the filtration membrane consists of a metal such as stainless steel, titanium, bronze, aluminum, or a nickel-copper alloy. In another embodiment, the membrane is composed of a material such as sintered stainless steel with an inorganic metal oxide coating, such as a titanium oxide coating.

In one embodiment, the deoiling zone comprises a membrane that is rapidly displaced in the horizontal direction. The retentate of the membrane comprises a fine catalyst and the permeate of the membrane comprises heavy oil. In particular, rapid displacement of the membrane in the horizontal direction includes rotation of the membrane.

In one embodiment, the filtration membrane operating pressure is in the range of 30-100 psi (about 2-7 bar). Filtration may be performed at a temperature of about 50-200 ° C. and a pressure of about 80-200 psi, such as a temperature of about 100 ° C. and a pressure of about 90 psi. In one embodiment, the deoiling zone comprising multiple filtration units is operated at a pressure in the range of about 20-400 psi, such as about 30-300 psi or about 50-200 psi. The pressure drop across the membrane in the filtration unit, referred to as the intermembrane differential pressure, is in the range of about 0-100 psi, such as about 0-50 psi or about 0-25 psi. In one embodiment, the temperature of the deoiling zone is in the range of about 100-500 ° F, such as about 150-450 ° F or about 200-400 ° F.

Solvent extraction

In the deoiling zone, an extraction medium is used for the extraction / separation of heavy oil from the catalyst used. In one embodiment, the extraction medium is a solvent or solvent mixture having a specific specific gravity of light, such as xylene, benzene, toluene, kerosene, reformate (light aromatic), light naphtha, heavy naphtha, light cycle Oil (LCO), medium cycle oil (MCO), propane, diesel boiling range materials and are used to "wash" the feed stream to the deoiling zone. In one embodiment, the solvent is a commercially available solvent, such as ShelSol ^™ 100 Series solvent.

In one embodiment, washing / mixing with the solvent (ie solvent extraction) is performed in a separate tank, such as a settling tank / mixing tank, prior to membrane filtration, eg, before the membrane filtration unit. In another embodiment, washing / mixing with solvents is done in-situ in the membrane filtration unit. In one embodiment, a feed stream comprising a light specific solvent and a slurry catalyst used is supplied in a separate stream to the one or more filtration units in a countercurrent manner. In another embodiment, washing / mixing with the solvent is in a coexistence manner.

In one embodiment, the solvent may be recycled solvent (solvent used) recovered from the process step in the deoiling zone. In another embodiment, a solvent mixture comprising at least any two of all the above solvents is used.

In one embodiment, the feedstock stream comprising the slurry catalyst, ie catalyst particles in heavy oil, is mixed / washed with the solvent in a volume ratio ranging from 0.10 / 1 to 100/1 (based on the catalyst slurry volume used). . In a second embodiment, the solvent is added at a volume ratio of 0.50 / 1 to 50/1. In a third embodiment, the solvent is added at a volume ratio of 1/1 to 25/1.

In one embodiment, the feedstock stream containing the slurry catalyst is mixed / washed with an amount of solvent sufficient to reduce the heavy oil concentration in the feedstock stream by at least 40%. In a second embodiment, a sufficient amount of catalyst is added to reduce the heavy oil concentration by at least 50%. In a third embodiment, the heavy oil concentration is reduced by at least 60%.

It is noted that with a decrease in heavy oil concentration, the catalyst particles sink to the bottom significantly faster (ie, as in a mixture of two phases). Thus, in one embodiment, washing / mixing with solvent is performed using a plurality of precipitation tanks, so that the solvent and the solvent from the precipitation tank until precipitation of catalyst particles at the bottom and most of the heavy oil is removed from the catalyst particles. Allowing continuous removal of the lighter phase comprising the heavy oil portion, leaving a stream consisting mostly of catalytic solids in a solvent having a specific specific gravity of light. In another embodiment, a precipitation tank is used in conjunction with a filtration unit, such as cross-flow filtration, cross-flow sedimentation, and the like, so that a portion of the heavy oil is phase separated from the catalyst particles by use of the precipitation tank, and then the remaining heavy oil undergoes filtration techniques. Separated using.

In one embodiment, after a sufficient amount of solvent is added to reduce the heavy oil concentration of at least 50%, a stream comprising solvent, catalyst particles and heavy oil is introduced into the settling tank to allow separation by gravity. In one embodiment, at least 90% of the heavy oil is removed from the catalyst particles after the continuous separation step using the plurality of settling tanks.

In one embodiment, the mixing of solvent and feedstock takes place at a time and temperature sufficient to prevent substantial asphaltene precipitation before and during filtration. In one embodiment, such temperature is in the range of about 50-150 ° C. In one embodiment, the mixing is in the range of 15 minutes to 1 hour. In another embodiment, the mixing takes place for at least 20 minutes. In another embodiment, in a continuous process, the mixing of solvent and feedstock takes place for less than 10 minutes. In another embodiment where the solvent and feedstock are mixed in-situ in the filtering device, the mixing occurs in less than 5 minutes.

In addition to binding / washing feedstock containing slurry catalyst in heavy oil using a solvent prior to filtration, the retentate of the membrane from the filtration process may also be washed with a solvent. After washing in the filtration unit, the permeate (filtrate) stream comprising the heavy oil and the solvent can be recovered in addition to the retentate stream to include an unsupported microcatalyst and solvent. The unsupported fine catalyst can then be separated from the retentate stream of the membrane.

In one embodiment, the solvent of the combined retentate-solvent stream is a different solvent than the solvent of the combined slurry-solvent stream. In another embodiment, the solvent used in the combined retentate-solvent may be the same solvent as the solvent of the combined feedstock-solvent stream. In another embodiment, the solvent may comprise a solvent from a source different than the solvent of the combined feedstock-solvent stream.

In one embodiment, the retentate stream obtained from the first filtration unit can be continuously combined with the solvent before the next filtration unit, through which the combined retentate-solvent stream is filtered. In one embodiment, the permeate (filtrate) stream of the later stage filtration unit (in a system with multiple filtration stages or units) is recycled and used as a solvent for use with the feed stream entering the initial stage filtration unit, Combined feedstock-solvent streams can be formed.

In one embodiment, the retentate stream is further diluted with a solvent enriched stream and passed to the next filtration unit. In one embodiment, the solvent enriched stream is a stream of unconverted oil with a solvent such as toluene and passes through the membrane of the next filtration unit. Once the retentate stream is moved to the subsequent filtration unit, the retentate stream can be sequentially washed in a countercurrent manner with a stream of toluene enriched through the membrane of the subsequent filtration unit.

In one embodiment, the retentate stream is washed sequentially in a “countercurrent” fashion, where the retentate stream passes next in one filtration unit while the solvent added to the retentate stream comes from one or more bottom filtration units. (Eg, 5-6 total steps). For example, in one embodiment, the solvent cascade from the last filtration unit to the first filtration unit is the reverse of the flow of the retentate stream through the filtration unit. In this way, the liquid portion of the feed to the original filtration unit comprises a mixture of solvent and unconverted oil, the liquid portion of the feed to the last filtration unit comprises substantially pure solvent and the retentate stream of the last filtration unit Comprises catalyst particles in a substantially pure solvent.

As shown in Figures 1A-1F, the filtration membranes used were (horizontal or vertical) pressure leaf units, plates and frame units (Figure 1A), corrugated membranes (Figure 1B), tube / hollow modules (1C). , A plurality of tube / hollow modules (FIG. 1D), a spiral 1E, or a combination thereof, such as a plurality of tubular modules (not shown) each being spiral.

1A is a cross-sectional view of a plate and frame (flat plate) unit. In one embodiment, the plate and frame (flat plate) unit may employ sheet stock filtration membranes.

In FIG. 1B, a pleated filtration membrane is sandwiched between two permeable sheets and wound over a core having a plurality of collection ports. An external guard is provided to protect the filtration membrane. The system is sealed by the end plate at opposite ends of the filter. Heavy oil is collected from the collection port and exits the outlet. In one embodiment of the pleated membrane of FIG. 1B, a sleeve is disposed around the cartridge and the housing, withdrawing the retentate stream from the bottom of the housing, whereby the cross-flow stream enters the pleats and moves tangentially with the membrane.

1C shows a substantially tubular membrane filter with an outer housing, inlet (feed), retentate outlet, and permeate outlet (filtrate). At least a tubular filter parallel to the axis of the housing extends in the housing.

1D is a second embodiment of a tubular filter system having a plurality of filter sleeves (hollow membrane tubes) arranged parallel to each other and also parallel to the axis of the housing.

1E shows a helical membrane module with alternating layers of membrane and separator screen wound around a hollow center core. In operation, the feed stream is injected into one end of the cartridge. The filtrate passes through the membrane and spirals into the core of the module, where it is collected for removal.

In one embodiment, the filtration assembly of deoiling comprises a plurality of filtration units for effective removal of heavy oil from catalyst particles. In one embodiment, the filtration assembly having a plurality of filtration units removes most of the heavy oil from the catalyst particles for the filtrate stream comprising the solvent and at least 90% of the incoming heavy oil (in the feed stream of the heavy oil and slurry catalyst). can do. In another embodiment, a filtration assembly having a plurality of filtration units can remove at least 95% of heavy oil from the catalyst particles. In a third embodiment up to 99% of the heavy oil is removed from the catalyst particles.

In one embodiment, the catalyst assembly comprises 2 to 10 filtration units. In another embodiment, at least four to eight filtration units are included. In a third embodiment, the assembly includes six filtration units. The filtration unit used in the deoiling zone can be any form of diafiltration, cross-flow filtration, dynamic filtration, cross-flow sedimentation, cocurrent sedimentation separation, countercurrent sedimentation separation and combinations thereof, these processes are described in more detail below. Will be.

In one embodiment of the membrane filtration process, each filtration unit comprises a plurality of stages, such as at least two stages of cross-flow filtration, at least two stages of diafiltration, or each of the independent stages of cross-flow filtration, cross-flow sedimentation. , Cocurrent sedimentation separation, countercurrent sedimentation separation, and / or combination of diafiltration and / or dynamic filtration. The number of filtration steps and the solvent to heavy oil ratio are set to achieve the required deoiling efficiency.

Jeong Yong Filtration

 In one embodiment, the membrane filtration is in the form of diafiltration. In the prior art, diafiltration is generally used for purification of retained high molecular weight species, increased recovery of low molecular weight species, buffer exchange and simple changes in the given solution properties. With the fractionation process of diafiltration and the use of a solvent, heavy oil molecules are washed through the membrane as filtrate, leaving catalyst solids (particles) in the retentate.

In one embodiment, diafiltration is in the form of a single step. In another embodiment, the diafiltration unit comprises a plurality of steps, for example at least some steps in one embodiment, about 2-5 steps in a second embodiment, at least 7 steps in a third embodiment. Include. With the use of diafiltration, the fine solids of the slurry catalyst in the first solution (eg heavy bleeding oil or hydrocarbon solution) are transferred to a second solution (retentate) along a solvent such as toluene or light naphtha. Heavy bleeding oil is recovered from the filtrate stream along the solvent.

Dynamic filtration

In one embodiment, one or more of the filtration units may be replaced with one or more dynamic filtration units.

Dynamic filtration has generally been used to treat wastewater, including particulate matter and waste oil. The dynamic filtration assembly has the ability to handle a wide range of materials, achieving remarkably high concentrations of retained solids, continuously operating over extended periods of time without the need for filter aids and / or backflushing, and evenly High filter performance is achieved to minimize overall system size. The dynamic filtration assembly may be in any suitable arrangement and will generally include a filter unit comprising one or more filter media, and a housing containing means for effecting relative movement between the filter medium and the material to be filtered. The means for effecting the relative movement between the filtration medium of the filter unit and the liquid to be filtered and the filtration medium can have any of a variety of suitable arrangements. Various suitable power means may be used to perform such relative motion, such as, for example, rotation, oscillation, reciprocation or vibration means.

Various vibration amplitudes and corresponding shear rates, oscillation frequencies, and shear strengths directly affect the filtration rate. Shear is produced by torsional oscillation of the membrane. In one embodiment of the dynamic filtration unit, the oscillation of the membrane occurs with an amplitude of about 1.9-3.2 cm peak to peak displacement at the edge of the membrane. Optimum filtration rates can be achieved at high shear rates, and since the concentrate is not degraded by shear, maximum shear is desirable within the limits of practical equipment. In one embodiment, the dynamic filtration unit generates at least about 20,000 shear forces per second. In a second embodiment, a shear force of at least about 100,000 per second is generated. In another embodiment, the oscillation frequency is about 50-60 Hz, such as about 53 Hz, producing a shear strength of, for example, about 150,000 per second. In another embodiment, a shear force of 20,000 to 100,000 is generated per second.

In one embodiment, the dynamic filtration assembly operates at a relatively low cross-flow rate, resulting in premature contamination of the membrane as it climbs up the equipment until the permeate rate drops to an unacceptably low level. Prevents significant pressure drop from (high pressure) to the outlet (low pressure) end.

In one embodiment, the operating pressure of the dynamic filtration assembly is generated by the feed pump. Higher pressures often increase the permeate flow rate, but higher pressures also use more energy. Therefore, the working pressure optimizes the balance between flow rate and energy consumption.

The dynamic filtration assembly can be any suitable device. Suitable cylindrical dynamic filtration systems are described in US Pat. Nos. 3,797,662, 4,066,554, 4,093,552, 4,427,552, 4,900,440 and 4,956,102. Suitable rotating disk dynamic filtration systems are described in US Pat. Nos. 3,997,447 and 5,037,562 and US Patent Application 07 / 812,123. Suitable oscillating, reciprocating, or vibratory dynamic filtration assemblies are generally described in US Pat. Nos. 4,872,988, 4,952,317, and 5,014,564. Other dynamic filtration devices are discussed in Murkes, "Fundamentals of Crossflow Filtration," Separation and Purification Methods, 19 (1), 1-29 (1990). In addition, many dynamic filtration assemblies are commercially available. For example, suitable dynamic filtration assemblies include Pall BDF-LAB, ASEA Brown Bovery rotary CROT filter and New Logic V-SEP.

In one embodiment, the dynamic filtration unit used is illustrated by New Logic's Shear Force Enhancing Vibration Process (V * SEP) system. In the V * SEP system, the membrane module is used for separation and a strong shear wave is added to the membrane surface. V * SEP systems have generally been used to treat wastewater, including particulate matter and waste oil. In one embodiment of the present invention, V * SEP is used in the deoiling process.

In one embodiment, dynamic filtration is used to allow the same separation efficiency to be achieved with fewer filtration steps. In particular, typical cross-flow filters are usually limited to a solids content of 25-35% by weight to prevent membrane contamination, but dynamic filtration machines can tolerate higher solids content (50-70% by weight) while maintaining performance. have. Thus, dynamic filtration can be used to reduce the number of steps required by removing more oil per step in diafiltration mode.

In the dynamic filtration unit, the slurry to be filtered moves in a freely flowing stream while remaining almost stationary. Shear cleaning activity occurs by horizontally displacing the membrane rapidly (ie, 50-60 Hz) (ie, in the direction coplanar with the membrane surface). In one embodiment, the displacement occurs by rotation or oscillating. Shear waves generated by displacement or vibration of the membrane cause solids and contaminants to rise to the membrane surface and remix with the slurry, exposing the membrane pores for maximum throughput.

In one embodiment, dynamic filtration is used to assist transport of catalyst (slurry) prior to heavy oil improvement. In another embodiment, dynamic filtration is used to concentrate the catalyst slurry to, for example, a solids content of about 60-70% by weight. In part, due to the concentrated catalyst slurry having a reduced volume compared to the catalyst slurry volume before concentration via dynamic filtration, the concentrated catalyst slurry can then be more easily transported to a heavy oil refinery site or reactor, where the heavy oil Prior to improvement, for example, it will be restored to a solids content of about 5% by weight.

Sedimentation separation

In one embodiment, the membrane filtration may be in the form of sedimentation separators. In sedimentation separation, the membrane is in the form of a plurality of channels arranged in parallel and the channels are inclined downward to promote sedimentation. In one embodiment, the channel is in the form of a corrugated membrane, eg, V-shaped, U-shaped, or the like. In another embodiment, the channel is in the form of a tube having an oval, square, rectangular or circular cross section. The term "channel" can be used interchangeably with "tube." In one embodiment, the sedimentation separator further comprises a receiving chamber (sedimentation container) for receiving the retentate.

In one embodiment, the filter system has a channel height or tube diameter of 100 mm or less, a length of about 0.2 to 2.5 m and an inclination angle of at least 45 ° from the horizontal surface. In a second embodiment, the tilt angle is in the range of 45 to 75 degrees. In another embodiment, the tube (or channel) has a length in the range of 0.2 to 1.5 m. In a fourth embodiment, the filter system has a tilt angle in the range of 30 to 60 degrees from the horizontal surface.

The tube can be in any shape or form. In one embodiment, the membrane filter is in the form of a plurality of channels having a rectangular cross section. In another embodiment, the membrane filter is in the form of a plurality of round tubes (circular cross section). In one embodiment, the tube (or channel) has a uniform cross section. In another embodiment, the cross section varies depending on the position of the tube.

In one embodiment of the membrane settling system, the apparatus includes a module comprising a tube (or channel), a cover plate and a return container (located below the sloped channel) for collection of the filtrate. In one embodiment, the apparatus further includes inlet and outlet chamber plates that enhance flow distribution. The plate may be a flat plate or a shaped plate. In one embodiment, the plates are arranged perpendicular to the inlet and outlet channels in close proximity.

Membrane sedimentation separators for use in the deoiling zone may be of any type: countercurrent sedimentation separators (shown in FIG. 2), cross-flow sedimentation separators (shown in FIG. 3) and cocurrent sedimentation separators (not shown). As shown in FIG. 2, which is an embodiment of countercurrent sedimentation separation, a feed stream and a solvent stream comprising slurry catalyst in heavy oil are provided to the receiving chamber as two separate opposed (backflow) streams. FIG. 3 shows an embodiment of a cross-flow sedimentation separator, wherein an inlet comprising a solvent, a slurry catalyst in heavy oil entering one side of the channel, and a filtrate (including heavy oil and solvent) on opposite sides of the channel Contains spills. A pyramidal receiving chamber is located below the channel for the collection of retentate (including slurry catalyst and solvent).

In one embodiment, the membrane filtration system comprises a plurality of different or identical settling separators, such as two consecutive cross-flow settling separators, a countercurrent settling separator and a continuous dynamic filtration system, or a cross flow settling, cocurrent settling, conventional Settling tank, if the vibration from the dynamic filtration unit does not propagate to the sedimentation basin / sedimentation unit, includes a combination of inclined sedimentation basins (vibration separation devices) with a dynamic filtration system.

In one embodiment, the feed stream to the membrane filtration unit, containing 60-95% by weight of heavy oil and 5-40% by weight of used catalyst (as solid, in the form of slurry catalyst) is 5 (as a solid) It can be present in the filtration unit as a retentate stream containing -40 weight percent catalyst, 0.01 to 1 weight percent heavy oil and the balance solvent. In a second embodiment, the retentate stream after the membrane filtration can contain anywhere from 0.05 to 0.5% by weight of heavy oil, based on solvent absence. In a third embodiment, the amount of heavy oil remaining in the retentate is in the range of 0.1 to 0.3% by weight.

In the deoiling zone, the slurry catalyst in heavy oil is solvent washed, separated in the mixed stream, solvent washed in the deoiling zone and transferred from the heavy USBO to the low boiling range solvent. The product obtained from the deoiling zone comprises a catalyst and a stream with a higher proportion of solvent and a stream without catalyst and with a relatively high proportion of USBO. From the deoiling zone, a stream of solvent and carrier oil mixture is sent to a fractionation column, where the top stream of solvent is recycled to the solvent tank for use in the washing process, and product recovery, hydrogenation process section, or another residue disposal. Create a bottom stream of carrier oil sent to the unit.

In one embodiment after membrane filtration (eg, cross-flow filtration, diafiltration, dynamic filtration, etc.), the filtrate product, including the solvent and heavy oil mixture, is separated from a separator, such as fractionation, for separation and subsequent recovery of the solvent and heavy oil. Sent to the column. The solvent (and any residual heavy oil) can then be separated from the catalyst particles in the retentate stream using various separation means including drying, detergent washing, ultrasonic washing, plasma washing, and the like. In one embodiment, a retentate stream comprising mostly slurry catalyst in a solvent can be sent to the drying zone.

In one embodiment, the fractionation column is a top stream of solvent that can be retransmitted to a solvent tank for reuse in a solvent wash process, and a carrier oil (unconverted heavy oil and that can be sent to a product recovery, hydroprocessing unit or residue disposal unit). A bottoms stream of heavier hydrocracked liquid product).

Dry area

In one embodiment, a retentate (bottom) stream consisting of used catalyst highly concentrated in solvent is sent to the drying zone for final liquefaction. Deoiling prior to drying causes sufficient hydrocarbon-dried material to be produced to meet the underlying metal recovery requirements.

In one embodiment, the feed stream to the drying zone comprises 50 to 90% by weight of hydrocarbon and the balance catalyst particles. Most hydrocarbons are in the form of solvents and the residual heavy oil comprises in one embodiment less than 5% by weight of the total stream, less than 3% by weight in another embodiment, and less than 0.1% by weight in another embodiment.

In one embodiment, the drying step may include, for example, evaporation at ambient conditions, warming in a dryer, or treatment through a robust thin film (or wiped film) bond type dryer or evaporator. In another embodiment, the drying step utilizes an apparatus, such as a nitrogen filled furnace, to convert the catalyst to a free flowing granule state by exposure to heat and reduced pressure for a minimum of time. In one embodiment, the drying apparatus includes an indirect firing kiln, an indirect firing rotary kiln, an indirect firing dryer, an indirect firing rotary dryer, an electrically heated kiln, an electrically heated rotary kiln, a microwave heated kiln, a microwave heated rotary kiln. , Vacuum dryer, thin film dryer, flexicoker, fluid bed dryer, shaft kiln dryer or any such drying apparatus. The retentate stream obtained from the filtration unit can be fed to the drying apparatus in co-current or countercurrent with a gaseous feed, which can be an oxidizing, reducing or inert gas.

In one embodiment, the drying apparatus is a thin film dryer, a thin film evaporator, a wiped film dryer, or a wiped film evaporator, which are efficient for rapidly exposing the catalyst particle surface to a heat transfer medium. In one embodiment, the drying apparatus is a vertical thin film dryer, a vertical thin film evaporator, a vertical wiped film dryer or a vertical wiped film evaporator. In another embodiment, the apparatus is a horizontal thin film dryer, a horizontal thin film evaporator, a horizontal wiped film dryer, or a horizontal wiped film evaporator. In a third embodiment, the appliance is a combi dryer (combining vertical and horizontal design) of LCI Corporation. Thin film or wiped film dryers / evaporators may operate in batch or continuous mode for a wide range of residence times depending on the layout of the dryer.

In one embodiment, the drying apparatus is a rotary kiln dryer, which can be a rotating inclined cylinder or a rotating heat exchanger. In one embodiment, the rotary kiln is one of a direct fired rotary kiln, an indirect fired rotary dryer, an electrically heated rotary kiln, and a microwave heated rotary kiln. The residence time of the rotary kiln dryer varies depending on the dimensions of the kiln and varies from 2 to 250 minutes.

In one embodiment, the drying treatment of the catalyst used is at atmospheric pressure. In a second embodiment, the pressure is from 0 to 10 psig. In one embodiment, drying takes place under nitrogen under inert conditions, such as a nitrogen flow in the range of 0.2 to 5 scf / min. In one embodiment, the nitrogen flow ranges from 0.5 to 2 scf / min. Other general conditions, ie temperature and residence time, can be varied depending on the organic material to be evaporated from the catalyst. In one embodiment, the residence time in the drying apparatus ranges from 5 minutes to 240 minutes. In a second embodiment, from 10 minutes to 120 minutes. In a third embodiment, at least 15 minutes. In a fourth embodiment, in the range from 30 minutes to 60 minutes. The treatment temperature may vary depending on the type of instrument used, the pressure applied and the level of heavy oil and solvent remaining in the catalyst used. In one embodiment using a vertical thin film dryer, the temperature is generally in the range of 300-450 ° F. (149-232 ° C.). In a second embodiment using a horizontal thin film dryer, the temperature is in the range of 400-700 ° F. (204-371 ° C.). In a third embodiment using a rotary kiln dryer, the temperature is in the range of 700 to 1200 ° F. (371 to 649 ° C.). In a fourth embodiment, the drying temperature is at a temperature high enough to decompose at least 90% of the carboxylates, ie surface active hydrocarbon compounds that can be bound to the catalyst particles. In a fifth embodiment, at least 95% of the carboxylates are removed with the use of a dryer.

In one embodiment, the drying step comprises at least two drying processes, wherein the second drying step is for removal of contaminants such as carboxylate, residual oil, etc. in the pore space of the catalyst used, for removal. The organic compounds are volatilized. In one embodiment, the retentate stream obtained from the deoiling zone containing the used catalyst highly concentrated in solvent is subjected to (at temperatures above 300 ° C., rotations of 0.5 to 10 rpm and residence times ranging from 5 to 200 minutes). Before being introduced into the rotary kiln dryer, it is first fed to a rotary drum dryer (operating at temperatures below 200 ° C.). The feed rate to the kiln is based on the diameter of the kiln. In one embodiment using a 6 ”diameter kiln, the feed rate to the kiln ranges from 2 to 10 lbs of solids per hour. In another embodiment using 18 ”kilns, the feed rate ranges from 10 to 300 lbs of solid material per hour.

In another embodiment, the retentate stream has an operating temperature in the range of 200-450 ° F. (93-232 ° C.) in the vertical section, a temperature in the range of 400-900 ° F. (204-482 ° C.) in the first half of the horizontal section. It is first dried in a combi dryer with a temperature in the range of 50-100 ° F. (10-38 ° C.) in half of the horizontal section (or cooling section). In one embodiment, the temperature of the stream leaving the combi dryer is in the range of 80-120 ° F. (27-49 ° C.).

In one embodiment, the drying zone comprises a plurality of drying mechanisms to maximize removal of carboxylates, residual oils, etc., in contaminants such as pore space of the catalyst used. In one embodiment, the retentate stream obtained from the deoiling zone is first fed to the combi dryer, and in one embodiment 0.1 to 1% by weight, in a second embodiment, 0.5% by weight in the second embodiment. For the effluent stream consisting essentially of residual heavy oil), most of the solvent is removed. In one embodiment, the combi dryer is maintained under a nitrogen blanket provided with nitrogen as a countercurrent flow in an amount of 0.2 to 5 scf / min. This dry powder is then sent to a second drying stage in a rotary kiln dryer, where residual organic material, such as heavy oil, is combusted. In a rotary kiln, nitrogen can be provided as a cocurrent or countercurrent flow. The residence time in the second step ranges from 10 to 150 minutes in one embodiment.

The volatilized organic compound after leaving the catalyst particles can be collected in a condenser so that heavy oil and / or solvent can be recovered.

Detergent washing

In one embodiment, instead of or in addition to a drying unit for removal of solvent / residue heavy oil in the catalyst (after membrane filtration), a surfactant is used to remove the solvent and / or heavy oil bound to the catalyst. The surfactant solution is added to the retentate stream coming from the membrane filtration unit. In another embodiment, the surfactant solution is added to the stream containing catalyst particles and hydrocarbons, ie solvents and residual heavy oil, coming from the drying zone.

In a mixing tank with a vessel, such as a mechanical agitation, the surfactant is solvent / and away from the solid catalyst used, with the hydrophilic head attracted to the water molecules and a hydrophobic tail that repels the water and adheres to the solvent and heavy oil. Draw any residual heavy oil. Opposing forces remove and loosen the solvent and heavy oil from the solid catalyst. The cleaning solution containing the surfactant and the mixture of catalyst and hydrocarbon used are mixed under sufficient time and conditions to remove the hydrocarbon from the catalyst surface into the aqueous solution. The mixture of surfactant / solvent / heavy oil in water can then be separated from the solid catalyst through known separation means including, but not limited to, decantation and the use of settling tanks.

In one embodiment, the mixing temperature ranges from about 30 ° C to 85 ° C. In a second embodiment, the mixing is at a temperature below 85 ° C. In a third embodiment, at a temperature up to 177 ° C. In one embodiment, the mixing (contacting) of the cleaning solution with the mixture of catalyst and hydrocarbon used is for at least 2 minutes. In a second embodiment, at least 5 minutes. In a third embodiment, at least 10 minutes.

In one embodiment, the surfactant is first dissolved in water, such as deionized water, at a concentration of about 0.001% to saturation. In a second embodiment, the surfactant is added at a concentration of 0.01% to about 10%. In a third embodiment, it is added at a concentration of 0.5% to about 5%. In a fourth embodiment, at least 90% of the hydrocarbons, ie solvents and heavy oils, are added at a concentration sufficient to dissolve and remove from the surface of the catalyst particles. In a fifth embodiment, the concentration of surfactant is sufficient to dissolve and remove at least 95% by weight of hydrocarbon from the catalyst particles.

In one embodiment, the surfactant is selected from anionic, nonionic, zwitterionic, acidic, basic, amphoteric, enzymatic and water soluble cationic detergents, and mixtures thereof. In one embodiment, the surfactant is an anionic detergent.

In one embodiment, the detergent is derived from water-soluble salts, in particular alkali metal, ammonium and alkanolammonium salts of organic sulfidation reaction products having alkyl groups having from about 8 to about 22 carbon atoms in the molecular structure and sulfonic acid or sulfuric acid ester groups. Anionic surfactant of choice (the term "alkyl" also includes the alkyl portion of the acyl group). Examples of such groups of synthetic surfactants are those obtained by the sulfate of alkyl sodium sulfate and potassium, in particular the higher alcohols (carbon number of C ₈ -C ₁₈ ) produced by the reduction of glycerides of tallow or coconut oil, C ₈ -C ₂₀ paraffinic sodium sulfonate and potassium, and alkyl benzene sulfonate sodium and potassium, in which the alkyl group comprises about 9 to about 15 carbon atoms in a straight or branched chain configuration.

In another embodiment, the anionic surfactant compound contains alkyl glyceryl ether sulfonic acid sodium, wherein the alkyl group comprises about 8 to about 12 carbon atoms, and about 1 to about 10 units of ethylene oxide per molecule. It is selected from the group consisting of sodium and potassium salts of alkyl phenol ethylene oxide ether sulfuric acid. In another embodiment, the anionic surfactant is selected from the group consisting of straight chain C ₁₀ -C ₁₂ alkyl benzene sulfonate sodium; C ₁₀ -C ₁₂ alkyl benzene sulfonic acid triethanolamine; Uji alkyl sodium sulfate; Coconut alkyl glyceryl ether sodium sulfonate; And sodium salts of sulfated condensation products of tallow alcohol with about 3 to about 10 moles of ethylene oxide; Alkyl sodium sulfate and potassium.

In one embodiment, the surfactant is a nonionic surfactant. Examples include water soluble ethoxylates of C ₁₀ -C ₂₀ aliphatic alcohols and C ₆ -C ₁₂ alkyl phenols.

In one embodiment, the surfactant is a semi-polar surfactant. For example, a water-soluble amine oxide containing one alkyl residue having about 10 to about 28 carbon atoms and two residues selected from the group consisting of 1 to about 3 carbon atoms; Water-soluble phosphine oxides containing two moieties selected from one alkyl group having about 10 to 28 carbon atoms and an alkyl group and a hydroxyalkyl group containing about 1 to 3 carbon atoms; And a water soluble sulfoxide containing one moiety selected from the group consisting of one alkyl moiety having about 10 to 28 carbon atoms and alkyl and hydroxyalkyl moiety having 1 to 3 carbon atoms.

In one embodiment, the surfactant is an amphoteric surfactant. By way of example, include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic moiety can be straight or branched, one of the aliphatic substituents comprising about 8 to 18 carbon atoms, at least One aliphatic substituent includes an anionic acceptor group.

In another embodiment, the surfactant is a zwitterionic surfactant. Examples include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, wherein the aliphatic moiety may be straight or branched, one of the aliphatic substituents containing about 8 to 18 carbon atoms, and one anion Sex receptors.

Plant-derived surfactants; Household detergents including natural oils such as orange oil, citrus oil, and the like; Commercially available degreasing agents; And conventional surfactants, including, but not limited to, conventional laboratory surfactants and detergents, such as alkyl sulfates, alkyl ethoxylate sulfates. In one embodiment, the surfactant is sodium lauryl sulfate (SDS), Brij detergent and niaproff anionic detergent. In another embodiment, the anionic detergent is a proprietary blend of straight chain alkylaryl sulfonic acid sodium, alcohol sulphates, phosphates and carbonates known as ALCONOX ^™ . In another embodiment, the surfactant is a detergent commercially known under the name LIQUINOX ^™ .

It is also envisioned that the surfactant does not need to be added as a cleaning solution. In one embodiment, the surfactant solution is produced in-situ by addition of a precursor material such as an alkali metal compound such as sodium hydroxide, ammonium hydroxide, so that at least the surfactant is in-situ for use in the detergent washing process. Is generated.

Ultrasonic cleaning

In one embodiment, in addition to or instead of the use of detergents for cleaning / removing solvents and heavy oils from the catalysts used, ultrasonic cleaning is used. Ultrasonic cleaning herein includes the use of high frequency sound waves (in the human listening area or in the range above about 18 kHz). In one embodiment, an ultrasonic transducer is used at a frequency in the range of 20 to 80 kHz. In a third embodiment, the frequency used is in the range of 15-400 kHz. In one embodiment, the ultrasonic tank is in one embodiment at a temperature of at least 50 ° C., in a second embodiment at least 70 ° C., to at least 6 ° C. below the boiling point of the solvent still remaining with the catalyst used. maintain.

In one embodiment, ultrasonic / acoustic energy is applied to the cleaning solution for less than 15 minutes. In one embodiment, 0.25 to 10 minutes are applied. In a third embodiment, the application is for less than 60 minutes. In one embodiment, organic components such as solvents and heavy oils attached to the catalyst particles are completely removed from the surface by implosion of bubbles caused by ultrasonic energy. In subsequent separation processes, such as cyclones, decanters or settling tanks, the deoiled fine catalyst particles can be collected separately from the bottom. The aqueous phase containing the solvent and heavy oil can be sent to the water treatment apparatus, the fractions rich in organic matter can be recovered and the water recycled to the detergent washing process as clean water. It is also possible to clean the wastewater by ultrafiltration, adsorption columns or other means before being reused as wash water in the detergent washing process.

plasma  washing

In one embodiment, in addition to or instead of using ultrasonic cleaning or at least a surfactant for cleaning / removing solvent and heavy oil from the catalyst used, plasma cleaning is used. In some embodiments, it is advantageous to use a plasma system as compared to conventional dryers, since a typical plasma jet is much hotter than a typical oil or gas burner. Thus, heat transfer depending on the energy source and the temperature of the material being heated is higher in the plasma process, thereby increasing the energy efficiency of the plasma process.

In one embodiment, the plasma cleaning process operates at a temperature of 400-900 ° C. (752-1652 ° F.) to volatilize residual hydrocarbons, ie, heavy oil residues and solvents in the catalyst particles. The volatilized organic compound after leaving the catalyst particles may be collected in a condenser and heavy oil and / or solvent may be recovered. The plasma reactor / vessel may be maintained under a blanket blanket or reduced atmosphere to allow recovery of the organic material after volatilizing the organic material as exhaust gas in the plasma reactor, and less than 0.5% by weight of hydrocarbons may be applied to the solvent material and / or Catalyst particles as dry powders contained as residual heavy oil are left.

In one embodiment, the plasma cleaning system includes a vessel (eg, a mixing tank or reactor), a plasma system for heating a mixture of catalyst particles and hydrocarbons in the vessel, and means for collecting the exhaust gas. In one embodiment, the plasma system includes a graphite electrode and an electric arc held between the graphite electrodes. In another embodiment, the plasma system includes a plurality of plasma torches located inside the vessel reactor. In one embodiment, a condenser system is used to collect and recover volatilized hydrocarbons. In another embodiment, a fractionation column is used to collect and separate the solvent from residual heavy oil in the volatized hydrocarbons collected from the plasma system.

Reference will now be made to the drawings to further illustrate embodiments of the invention.

In one embodiment of the deoiling zone as shown in FIG. 4, the feedstock stream 1 into the deoiling zone 200 enters the slurry drum 100 so that the feedstock 1 is stored and the slurry pump ( 150) continuously. Feedstock 1 leaves the slurry drum 100 via line 2, passes through slurry pump 150, and slurry pump 150 moves feedstock 1 to the operating pressure of the deoiling zone 200. Pump. In order to shake the feedstock and prevent the agglomeration of catalyst particles in the slurry drum 100, a portion of the feedstock of line 2 is recycled to line slurry slurry 100 via line 3. The major part of the feedstock of line 2 continues to the deoiling zone 200, but immediately before entering the deoiling zone 200, the feedstock 1 is enriched with a light hydrocarbon solvent 4, for example toluene. Mixed with the stream to dilute the unconverted residue hydrocarbon oil and form stream 5 which is fed to the deoiling zone 200.

In one embodiment, the light hydrocarbon solvent 4 is toluene. In the deoiling zone 200, the unconverted oil is removed from the catalyst particles in the stream 5, leaving a stream 6 consisting essentially of the unconverted oil in a light hydrocarbon solvent such as toluene. Stream 6 is sent to heat exchanger 250 to form a heated stream 7 which enters separator 300 so that the flashed off top is toluene vapor stream 8, Unconverted oil is removed as stream 9. In one embodiment, separator 300 is a distillation column in order to achieve a clear separation between solvent and recovered oil. The stream 9 comprising unconverted oil can be recycled to a heavy oil refinery process, such as a reduced pressure residue unit or sent to a product reservoir for further processing. Stream 14 from the deoiling zone 200 consists of catalyst particles, carbon fines and metal fines, with the stream 6 consisting of unconverted oil in toluene missing. Stream 14 proceeds to drying zone 500 where toluene vapor stream 16 is separated from catalyst, carbon fines and metal fines (ie, hydrocarbon-free solids) in stream 17. The drying zone may be an evaporation and solid liquefaction apparatus known to those skilled in the art. In one embodiment (not shown), stream 17 is sent to a metal recovery system so that the metal in the catalyst can be recovered and subsequently used in a catalytic synthesis unit.

The toluene vapor streams 8 and 16 are combined into a combined toluene vapor stream 31 and enter the condensation unit 350, and the toluene is converted from the vapor state to the liquid state and leaves the condensation unit as the liquid toluene stream 11. The liquid toluene stream 11 enters the solvent storage drum 400 from which toluene is recycled via line 13 to the deoiling zone 200. Since a small amount of toluene is lost through vaporization, an additional toluene stream 12 is added to the solvent storage drum 400.

In yet another embodiment of the deoiling system as shown in FIG. 5, stream 14 from deoiling zone 200, consisting of catalyst particles, carbon fines and metal fines missing stream 6, is slurry concentrated zone 550. ), From which a portion of stream 14 (stream 19) is fed to drying zone 500, and a portion of stream 14 is fed through line 18 to dry zone 500. From toluene vapor stream 16 from the mixture.

In another embodiment as shown in FIG. 6, before the feedstock stream 1 (including the catalyst used in heavy oil) 1 is mixed with the light hydrocarbon solvent 4, the line 2 is in a slurry concentration zone ( 600, from which the unconverted oil 21 is removed. Stream 22 (ie, feedstock 1 without unconverted oil 21) is then mixed with light hydrocarbon solvent 4 and fed to the deoiling zone 200.

FIG. 7 shows a deoiling system as shown in FIG. 2, further comprising slurry concentration zone 550 (as shown in FIG. 5) and slurry concentration zone 600 of FIG. 6.

Referring to FIG. 8, the feedstock 51 is mixed with the light hydrocarbon solvent 54 to form a stream 55, which consists of a membrane 215 separating the upper section 210A and the bottom section 210B. Fed to the first filtration unit. In general, stream 55 enters the tube side of the multi-tube bundle of membrane elements and permeate stream 56 exits the shell side of the membrane housing. In the following, the light hydrocarbon solvent 54 is a toluene enriched stream (ie, permeate obtained from the second stage of filtration). Slurry pump 230 maintains a constant velocity in the tube to prevent precipitation or agglomeration of catalyst particles. A portion of unconverted oil with toluene passes through membrane 215 to bottoms section 210B and exits first filtration unit as stream 56 to recover toluene and unconverted oil as a separate stream. To the distillation process. Retentate stream 57 is diluted with toluene enriched stream 58 to form stream 59, which is directed to a second filtration unit. The second filtration unit consists of a membrane 225 separating the upper section 220A and the bottom section 220B. Slurry pump 240 maintains a constant velocity in upper section 220A above membrane 225 and allows stream 59 to continue to move, thereby preventing precipitation or agglomeration of catalyst particles. A portion of unconverted oil with toluene passes through membrane 225 to bottoms section 220B and exits the second filtration unit as stream 54, which is recycled and mixed with feedstock 51, Form stream 55.

9 illustrates an embodiment of a deoiling zone using a precipitation tank system 70 for pre-mixing / washing catalyst slurry obtained from a heavy oil refinery system. The feed solvent to the precipitation tank may be solvent recycled from any drying zone 20 or solvent recovery system 50. In one embodiment, some (or all) filtrate from the filtration unit is recycled back to the settling tank 70 as shown. In another embodiment, some (or all) of the retentate is recycled back to the settling tank 70 as shown. In another embodiment (not shown), solvent recycled from the recycle zone can also be diverted to a settling tank for use in washing feed streams comprising slurry catalyst in heavy oil.

10 illustrates an embodiment of a system having a two stage dry zone. The first drying zone may be any of a rotary dryer, a vertical thin film dryer, a horizontal thin film dryer, or a combination dryer (vertical and horizontal combination). As shown, the filtrate from the membrane filtration unit comprising the solvent and heavy oil is transferred to a solvent recovery unit. In this unit, the solvent condenses into the liquid stream and moves to the solvent tank. In one embodiment, the solvent recovery unit includes a distillation column to achieve clear separation between solvent and heavy oil. Heavy oil may be recycled to the vacuum residue unit or sent to the product reservoir for further processing. In the first drying step 20, the retentate stream 2 obtained from the filtration unit is substantially concentrated, for example, for a stream comprising less than 0.2% by weight of heavy oil, up to 90% by weight of solvent and the balance solid catalyst, Converted to a substantially dry powder form containing up to 1% by weight of heavy oil. The solvent vapor stream may be recovered (condensed) and recycled back to the membrane filtration unit or settling tank (not shown) for mixing with the feed stream to the filtration unit.

For example, in a second drying step, such as a rotary kiln dryer, the organic material is substantially evaporated for a stream consisting essentially of a dry powder of the used catalyst comprising metal and carbon fines.

Metal Recovery from Dry Powder Catalyst

In one embodiment, the dry powder of the catalyst used is sent to a metal recovery unit for recovery of precious metals such as molybdenum, nickel, chromium, etc. for later reuse in the catalyst synthesis unit. In one embodiment, the deoiled and dried particles of the catalyst used are first leached into an aqueous solution comprising ammonia and air in an autoclave, i.e., a multi-chamber vessel shaken at sufficient temperature and pressure, wherein ammonia and Air is supplied to induce a leaching reaction and the Group VIB metals (eg molybdenum) and Group VIII metals (eg nickel) are leached into a solution that forms Group VIB and Group VIII water soluble metal complexes.

The leached slurry is then subjected to a liquid stream ("PLS" or pressure leach solution comprising Group VIB and Group VIII metal complexes, through physical methods known in the art, such as precipitation, centrifugation, decantation, filtration, or the like. ), And liquid-solid separation as a solid residue comprising coke and any Group VB metal (vanadium) complex. Following liquid-solid separation, the pH of the PLS stream is controlled to the level at which the selective precipitation of the metal complex occurs (“pre-selected pH”), so that at least 90% of the Group VIB metal, Group VIII, initially present prior to precipitation At least 90% of the metal and at least 40% of the Group VB metal are allowed to precipitate. In one embodiment, the metal complex undergoes further processing / pre-selected pH conditioning to further recover Group VIB and Group VIII metals as metal sulfides, which can then be used in catalytic synthesis units.

< Example >

The following exemplary embodiments are intended as non-limiting.

Cross-flow filtration Example

The feedstock (1-10 μm) of the spent residue hydrogenation process slurry phase catalyst in the unconverted heavy oil product was treated using eight stages of cross-flow filtration. Cross-flow filtration was performed at 175 ° C., 75 psig. The feed slurry solids content was 12% by weight. In each step, the feed oil was diluted with toluene equivalent to the original feed slurry. The resulting mixture was recycled through a cross-flow filtration module until sufficient oil and toluene permeated through the membrane to produce a 25% wt solid concentrated slurry. To prevent membrane fouling, the recirculation pump was maintained at a sufficient speed (greater than 10 feet per second) through the filter housing tube.

The design of the membrane allowed only oil to permeate through the tube wall to the shell side of the bundle and fine solid catalyst retained on the tube side. This process was repeated an additional seven times to transfer the catalyst to the substantially oil-free toluene stream. The toluene slurry obtained was evaporated in a combined vertical thin film / horizontal dryer to produce a dry solid. The hottest zone in the dryer was operated at a temperature of 550 ° F. Less than 0.5% by weight of toluene extractable oil in the dry solid was analyzed, indicating that at least 99.9% of oil was removed. This material was found to be deoiled enough to allow recovery of the active metal using an aqueous leaching process. Analysis of the permeate oil stream indicated that no detectable levels of molybdenum were present, confirming that the molybdenum-based catalyst was recovered quantitatively into a clean toluene slurry.

The single stage cross-flow filtration membrane module is operated eight times in sequence to work like an eight stage cross-flow system. However, because each step was cross-flow and aimed at a very high degree of deoiling, very large amounts of toluene (7.75 times the fresh slurry ratio) were used. In one embodiment, if toluene is added only in the last step, and the toluene permeate flows to the previous step, it will probably require 5 or 6 steps (and 2-3 times the toluene rate of the new slurry rate).

Dynamic filtration Example

The catalyst in oil exchanged with toluene was tested at 100 ° C. (temperature calibration basis). 20 gallons of catalyst / oil slurry feed were tested. First, the solid was concentrated in oil, and then the solid was washed or diafiltered in the oil slurry using toluene as washing solvent (ie, the oil was exchanged for solvent). The catalyst / oil slurry that could be pumped included 14 weight percent catalyst solids and other solids and 86 weight percent oil. In one embodiment, the oil is removed and replaced with toluene until the oil concentration is less than about 2% by weight.

Specifically, toluene was used as an alternative solvent to replace the oil and to keep the total solids at a pumpable level. Any permeate containing oil or toluene can be sent to the distillation column for recovery. The final washed catalyst solids can be further processed using another technique. Only oil, toluene and soluble solids will pass through the membrane and the catalyst solids will be retained. Thus, a catalyst slurry in a liquid phase with reduced amount of oil is produced, which is suitable for further processing steps. In one embodiment, at least about 95 weight percent solids is recovered in the final washed concentrate (retentate). Heating equipment was used and the feed liquid was processed using a sealed nitrogen purging tank.

The evaluation was performed by separating as many variables as possible to determine the optimal variable. Variables included membrane type, temperature, pressure, concentration factor and contamination. The parameters were evaluated as follows.

Large particles were removed by pre-screening the sample material using a 100-mesh screen and then placed in a feed tank connected to a New Logic Series L V * SEP machine. The membrane was installed, feed introduced and pumped into the Series L V * SEP machine.

Step 1. Membrane Test

Membrane tests were used to evaluate the various membranes for the sample material to determine the optimal membrane in terms of flow rate and / or permeate quality. The performance was measured in "recycle mode", which means that the material is not concentrated and the separated stream is returned to the feed tank and only the relative performance of each membrane is measured under the same conditions. An exemplary "recycle mode" is shown in FIG. 11.

Step 2. Pressure Test

The pressure test was used to determine the optimal pressure of the selected membrane for the particular feed material. Permeate velocity was measured while gradually increasing the pressure in the system. The pressure test measures whether it is possible to reach a point where the increased pressure does not result in a significant increase in permeate flow rate, and at what pressure the increase in pressure no longer results in a significant increase in permeate flow rate. It was.

Step 3. Long-Term Line-Out Test

Long-term line-out tests were used to determine whether permeate velocity was stable over time by measuring the flow rate over time. The long term line-out test was a long term test to confirm that the system would lose flow, such as a tubular cross flow system. The results of the long term line-out test can also be used to determine the frequency of cleaning if necessary.

Step 4. Wash Test

To assess the average flow rate for each individual wash, a wash test was designed to measure the flow rate for the wash volume. Since the membrane area of the Series L V * SEP machine was only 0.5 square feet, the wash test was completed in batch mode. Permeate was continuously removed from the system while the concentrated material was returned to the feed tank. The washes were added one at a time and one wash was completed when the same amount of permeate was removed compared to the added wash water. In the wash test, one continuous wash was completed in batch mode. Once the permeate was removed, additional toluene was added to the tank.

Step 5. Concentration Test

If not obtained in the wash test, the concentration test was designed to concentrate the solid to the desired end point. Since the membrane area was only 0.5 square feet, the concentration test was completed in batch mode. Permeate was continuously removed from the system while the concentrated material was returned to the feed tank. The data obtained was used to measure the average flow rate over the concentration / recovery range, which in turn allowed to determine the preliminary system scale.

Test conditions include a temperature of about 90-100 ° C. (temperature calibrated to 100 ° C.), a pressure of about 100-120 psi for the membrane test and a pressure of 90 psi for the wash test, a sample size of 20 gallons, and 0.5 as described above. Square feet of membrane area were included.

Result-Membrane Selection

Two membranes with good chemical resistance and capable of withstanding high temperatures, as detailed in Table 1, were selected for testing.

Tested membrane membrane type Handwork size Temperature Water flow rate * Halar ^® on Teflon ^® Fine filtration 0.05μm 200 ℃ 500 gfd Teflon ^® on Woven Glass Fiber Fine filtration 0.1 μm 200 ℃ 750 gfd

Average batch cell test results for new membranes at 60 psi and 20 ° C

The relative performance of each of the selected membranes was tested. Sample feed material was prepared in the feed tank and the system was placed in "recycle mode". Each of the membranes described above was set up and a "line-out test" of 2-4 hours was performed. Membranes were compared based on flow rate and permeate quality. Table 2 shows the relative performance of each membrane.

Membrane Selection Results membrane Initial flow * Terminal flow pressure Halar ^® on Teflon ^® 42.6 ml / min 47.8 ml / min 100 psi Teflon ^® on Woven Glass Fiber 25.8 ml / min 11.7 ml / min 120 psi

Temperature calibrated to 100 ° C

12 is a graph depicting membrane test results. The operating temperature was 100 ° C. Factors used for membrane selection include, for example, flow rate, permeate flow rate, filtrate quality, chemical compatibility of the membrane, mechanical strength of the membrane, and high temperature resistance of the membrane. Teflon ^® film of 0.05μm exhibited good flow rate than Teflon ^® film of 0.1μm. Analysis of the filtrate obtained from each test result, while the Teflon ^® of 0.05μm film comprising a solid dispersion of 181ppm of the filtrate was found to contain a total of dispersion solids of only 72ppm film of 0.1μm Teflon ^®. The feed slurry comprised 9.18 wt% solids and 90.82 wt% oil. Thus, a 0.05 μm Teflon ^® membrane provided a better flow rate, but the permeate quality was poor.

In addition to good flow rate or permeate quality, the membrane must be durable and able to remain effective in the feed material. Many materials are available for membrane construction, which is still an optimization technique available. In addition to the membrane itself, the compatibility of all other wetted parts should be tested. Halar ^® (ethylene chlorotrifluoro-ethylene) and woven glass fiber materials are both chemically inert and will be compatible with toluene and oil carriers. In addition, they will all be able to withstand 100 ° C. process temperatures. In terms of chemical compatibility and temperature tolerance categories, the membranes are essentially equivalent.

However, the film in terms of mechanical strength, a woven fiberglass support material will withstand much stronger and better over the long run than Halar ^®. Thus, were selected for further analysis film is 0.1μm Teflon ^® on the woven glass fiber.

Pressure selection

The result of the pressure test is shown in FIG. The operating temperature was 100 ° C. The optimum pressure was determined by measuring the flow rate at various pressures. Since the flow rate was the largest at 90 psi, 90 psi was the optimal pressure.

Initial concentration

The system was first started in "recycle mode" and the optimum pressure and expected process temperature were set. The system was run for several hours to verify that the flow rate was stable and the system had reached equilibrium.

The permeate line was then bypassed to a separate container to allow the system to operate in "batch" mode. Permeate flow rates were measured at appropriate time intervals to determine the flow rates produced by the system at various levels of concentration. As the permeate was removed from the system, the solid concentration in the feed tank rose. 14 illustrates batch mode operation.

Initial concentration reduces the feed volume by removing oil and concentrating the solids. As a result, less washing solvent can be used. No wash solvent was added and only the initial solid was concentrated.

Table 3 shows the mass balance results of the initial concentration.

Mass balance results Initial volume Terminal volume collection% Initial solid% Terminal solid% 20 gallons 11.7 gallons 41.49% 9.18% 15.69%

Initial concentration is at a pressure of about 100 ° C. and about 90 psi. Further concentration could be performed, but after the initial concentration, the feed was very viscous and the flow rate was relatively low due to the viscosity. The addition of toluene was thought to reduce the viscosity and greatly improve the flow rate. Concentration was stopped at about 41% recovery because significant volume reduction occurred, the solid fraction increased to an appropriate level, and toluene addition could improve the flow rate.

Table 4 shows the system performance at initial concentration.

Initial concentration result Initial flow Terminal flow Average flow pressure Temperature 34.5 gfd 28.2 gfd 29.6 gfd 90 psi 100 ℃

Jeong Yong Filtration  fair

If the feed volume was reduced by 41% and left approximately 11.7 gallons of feed remaining, the system layout was preserved, allowing the permeate to be diverted to a separate container and the reject line returned to the feed tank. In addition, clean toluene was added to the feed tank by filling the top to maintain tank level and replenish the feed volume when removed to the filtrate.

The process continued for several days. During the wash study, nine small amounts of samples were taken in permeate and concentrate at different times throughout the wash test. After about 75 gallons of solvent were added, the washing process was stopped. At first, the filtrate was very dark and oily. As the washing process continued, the filtrate faded to a very light amber color. Table 5 shows the mass balance results during diafiltration.

Diafiltration Material Balance Results ID time Removed filtrate Cleaning volume Permeate solid Discarded solid One 165 minutes 1.8 gallons 0.1x 1 ppm 9.77% 2 301 minutes 3.1 gallons 0.3x 3 ppm 9.88% 3 906 minutes 10.3 gallons 1.0x 153ppm 4.62% 3a 1117 minutes 12.5 gallons 1.3x 4 ppm 11.31% 4 2362 minutes 38.3 gallons 4.0x 1500 ppm 7.86% 5 2974 minutes 58.0 gallons 5.7x 406 ppm 24.51% 6 3122 minutes 61.1 gallons 5.9x 481 ppm 41.33% 7 3180 minutes 61.9 gallons 6.0x 137 ppm 38.58% 8 3430 minutes 71.9 gallons 6.9x 21 ppm 25.01% 9 3983 minutes 80.3 gallons 7.6x 32 ppm 42.41%

Prior to testing, six wash volumes were evaluated to be sufficient to theoretically “clean” the solids and remove sufficient oil. During the course of the test, about 75 gallons of clean toluene were used. Diafiltration was stopped after the toluene supply was exhausted and after at least six washes were completed. The final volume was concentrated until the feed slurry became quite thick. Concentration was stopped when the slurry became quite thick and there was a risk of clogging.

15 is a graph of diafiltration test. Process conditions included Teflon ^® on a woven glass fiber membrane having a temperature of 100 ° C., a pressure of 90 psi and a pore size of 0.1 μm. The mean flow rate plot includes data from initial concentration, not shown. The actual average flow rate was 112 gfd during the test.

Several observations were made during the test: 1) Nonwoven glass fiber drainage ("Manniglass") was mechanically unbearable; 2) the nylon "Tricot" drainage was well tolerated; 3) the polypropylene drainage operated to an acceptable degree but swelled; 4) When the system is not running, solids will settle in the tubes and block the system; 5) good pre-screening is needed to prevent clumping; 6) no significant H ₂ S was present in the sample (300 ppm initially present but removed); 7) the flow rate was low on the oil, but improved significantly with the addition of toluene; 8) Viton ^® elastomers swelled poorly and did not work many times; 9) low cross-flow accumulated solids in the filter head; 10) The cake layer accumulated on the film surface.

As mentioned above, the filtrate was initially dark but dark. At the end of diafiltration, the color turned pale amber. There have been several cases in which the filter head disintegrates during the test, replacing leaking Viton ^® seals and inoperable drainage material. Each time the filter head was opened, the permeate chamber was contaminated with feed slurry. When the operation resumes, the filtrate will initially be slightly turbid and then purged as the contamination is cleaned. A large difference was observed in the solid ratio of the filtrate. Without wishing to be bound by theory, it is believed that the large change observed in the solid ratio of the filtrate can be explained by permeate chamber contamination.

6 shows the permeate quality after membrane change.

ID Total time Delta time Permeate solid 2313 minutes 0 min Change of membrane 4 2362 minutes 49 minutes 1500 ppm 2792 minutes 0 min Change of membrane 5 2974 minutes 182 minutes 406 ppm 6 3122 minutes 330 minutes 481 ppm 7 3180 minutes 388 minutes 137 ppm 8 3430 minutes 638 minutes 21 ppm 9 3983 minutes 1191 minutes 32 ppm

The membrane itself should be able to hold a significant proportion of solids. Solids in the permeate may not be the result of solids that have passed through the membrane pores. Rather, contamination can contribute to solids in the filtrate. In addition, the swollen Viton ^® O-ring could at best provide a slight seal. Each time the membrane was changed, a new set of O-rings was installed. If there is no contamination in the permeate chamber and the O-ring seal is good, the solids in the filtrate can range from about 10-20 ppm.

Another possible explanation for solids in the filtrate is the distribution of pore sizes in the membrane. In particular, although the membrane has a nominal pore size rating, the actual pore size varies for any given membrane. The pore size distribution curve takes the form of a bell curve. The nominal pore size rating is usually the average of all sizes. Thus, membranes with a nominal pore size rating of 0.1 μm may have pores as large as 1.0 μm. When measuring the particle size distribution of the catalyst solids, there may be some overlap, as shown in FIG. 16.

Teflon ^® membranes of 0.05 μm or smaller grade may be too large to remove all solids at all. Smaller membranes with a pore size lowered to 0.01 μm and made of other materials including polyvinylidene difluoride (PVDF; Kynar ^® ) may have good solids removal capability, but such membranes have lower chemical and temperature resistances resulting in time Durability over time may be low.

System with integrated cross-flow filtration & combination drying unit

A slurry feed stream (100 lbs / hr) obtained from a heavy oil refinery unit is provided. The stream contains 20 lbs of spent catalyst in 80 lbs of heavy oil, which is an unconverted heavy oil / heavy hydrocracked product. About 300 lbs of solvent is also provided to the cross-flow filtration unit. The cross-flow filtration unit includes a plurality of filter stages with the operating conditions shown in Table 7.

Filter steps Temperature (℉) Pressure (psig) One 200 30 2 200 50 3 200 70 4 200 90 5 200 110

The retentate stream (100 lbs) obtained from the cross-flow unit comprises 20 wt% used catalyst, 79.9 wt% solvent such as toluene, and 0.1 wt% heavy oil and is sent to a continuously connected drying zone. The filtrate stream contains approximately 220.1 lbs of solvent and 79.9 lbs of heavy oil and is sent to a solvent recovery unit.

The drying apparatus used in the first stage of the drying zone is an LCI combination dryer heated indirectly with steam or hot oil, 232 ° F. in the vertical section, approximately 800 ° F. in the first half of the horizontal section, and the last half of the horizontal section (or the cooling section). ) Has an operating temperature of 70 to 77 ° F. The combi dryer is maintained at a pressure in the range of 0 to 10 psig and the countercurrent nitrogen flow is maintained at a range of 0.5 to 1 scf / min. The dry powder catalyst exiting the combi dryer is in the temperature range of 100 to 110 ° F. and residence time in the apparatus is 10 to 120 minutes. The oil content in the dry catalyst powder is measured using TGA (thermogravimetric analysis), which shows a heavy oil concentration of less than 0.5% by weight.

System with cross-flow filtration & two stage drying unit

The previous example is repeated with the addition of a rotary kiln dryer in series with the combi dryer. The dry powder obtained from the combi unit is sent to a rotary kiln dryer in the range of 4 to 6 lbs per hour. The kiln is operated at a temperature of about 800 ° F., kiln rotation of 1 to 5 rpm, and residence time of 30 to 60 minutes. Nitrogen flow is cocurrent in a rotary kiln. TGA analysis indicates that the oil concentration in the powder exiting the kiln is in an amount of less than 0.1% by weight, and in one embodiment, less than 0.05% by weight.

For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers indicating quantities, percentages, or ratios, and other numerical values, as used herein and in the claims, may be changed in all instances by the term "about". It should be understood that there is. Accordingly, unless indicated to the contrary, the numerical variables set forth herein and in the appended claims are approximations that may vary depending upon the desired properties sought to be achieved by the present invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates it to one explicitly. Herein, the term "comprising" and its grammatical variations are intended to be non-limiting, so that the description of an item in a list is not intended to exclude other similar items that may replace or be added to the listed item.

The description herein uses examples, including the best mode, to disclose the invention and for any skilled person to make and use the invention. The patentable scope is defined by the claims, and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to fall within the scope of the claims if they have structural elements that do not differ from the literal description of the claims, or if they include equivalent structural elements that do not materially differ from the literal descriptions of the claims. . All citations referred to herein are expressly incorporated herein by reference.

Claims (73)

For receiving a feed stream comprising a catalyst particle in heavy oil and a solvent, said feed stream having a plurality of filtration units for removing at least 90% of said heavy oil from said catalyst particle, said feed stream being removed with (a) solvent A filtration assembly for separating into a filtrate stream comprising heavy oil and (b) a catalyst stream having a reduced heavy oil content and a retentate stream comprising a portion of said solvent;
A separator for receiving the filtrate stream and for separating the heavy oil from the solvent; And
Catalyst particles in a feed stream comprising 5-40 wt% catalyst particles in heavy oil, comprising means for recovering the catalyst particles as a dry powder containing less than 1 wt% heavy oil and solvent from the retentate stream. System to separate heavy oil from oil. The method of claim 1,
Wherein said plurality of filtration units are selected from cross-flow filtration, diafiltration, dynamic filtration, cross-flow sedimentation, cocurrent sedimentation separation, countercurrent sedimentation separation, and combinations thereof. A feed stream comprising catalyst particles in heavy oil and a solvent, wherein at least 90% of the heavy oil is removed from the catalyst particles to contain a filtrate stream containing heavy oil in solvent and the feed stream A filtration assembly for producing a retentate stream having a heavy oil concentration lower than the heavy oil concentration in the reactor, wherein at least one of the filtration units is subjected to dynamic filtation with a shear force of at least about 20,000 / second;
A separator for receiving the filtrate stream and for separating the heavy oil from the solvent; And
From catalyst particles in a feed stream comprising 5-40% by weight catalyst particles in heavy oil, comprising means for recovering catalyst particles as a dry powder containing less than 1% by weight heavy oil and solvent from the retentate stream. System for separating heavy oils. The method of claim 3,
Wherein said dynamic filtration is vibratory dynamic filtration. The method according to claim 3 or 4,
Wherein said dynamic filtration has a shear force of 20,000 to 100,000 / sec. The method according to claim 3 or 4,
Wherein said dynamic filtration has a shear force of at least about 100,000 / second. Filtration assembly comprising a plurality of channels arranged in parallel and having at least one filtration membrane having an inclination angle of at least 45 degrees from a horizontal plane, the membrane comprising (a) at least 50% of the solvent and the heavy oil in the feed stream. (B) a mean pore size selected for separation into a filtrate stream comprising (b) a catalyst particle having a reduced heavy oil content and a retentate stream comprising a portion of said solvent;
A receiving chamber for receiving the retentate stream;
A separator for receiving the filtrate stream and for separating the heavy oil from the solvent; And
From catalyst particles in a feed stream comprising 5-40% by weight catalyst particles in heavy oil, comprising means for recovering catalyst particles as a dry powder containing less than 1% by weight heavy oil and solvent from the retentate stream. System for separating heavy oils. The method of claim 7, wherein
And the plurality of channels have an inclination angle of 45 to 70 degrees from the horizontal plane. The method of claim 8,
The heavy oil separation system, characterized in that the plurality of channels in the form of a tube having an ellipse, square, rectangular or circular cross-sectional area. The method according to any one of claims 7 to 9,
Wherein the filtration sedimentation assembly is one of a countercurrent sedimentation separator, a cross-flow sedimentation separator and a cocurrent sedimentation separator. The method according to any one of claims 1 to 10,
The heavy oil separation system, wherein the feed stream contains 10-30% by weight of catalyst particles as a solid. The method according to any one of claims 1 to 11,
And a settling tank at least before the filtration assembly to remove at least a portion of the heavy oil from the feed stream. The method according to any one of claims 1 to 12,
A heavy oil separation system, wherein the filtration assembly has at least two filtration units. The method according to any one of claims 1 to 13,
And the filtration assembly removes at least 95% of the heavy oil from the catalyst particles. The method according to any one of claims 1 to 14,
And the filtration assembly removes at least 99% of the heavy oil from the catalyst particles. The method according to any one of claims 1 to 5,
And wherein the filtration assembly comprises at least a filtration membrane having an average pore size of less than 5 microns. The method according to any one of claims 1 to 16,
And wherein the filtration assembly comprises at least a filtration membrane having an average pore size of less than 1 micron. The method according to any one of claims 1 to 17,
And wherein the filtration assembly comprises at least a filtration membrane having a sufficient average pore size through which at least 50% of the heavy oil can pass and exit with the filtrate. The method according to any one of claims 1 to 18,
And a drying zone for recovering the catalyst particles as a dry powder containing the solvent and volatilizing the heavy oil and less than 1% by weight of heavy oil. The method of claim 19,
The drying zones are indirect fired kilns, indirect fired rotary kilns, indirect fired rotary kilns, indirect fired rotary dryers, electric heated kilns, electric heated rotary kilns, microwave heated kilns, microwave heated rotary kilns, decompression dryers, thin film dryers, flexicokers, fluidized beds A heavy oil separation system comprising at least a drying device selected from a dryer, a shaft kiln dryer, a thin film evaporator, a wiped film dryer and a wiped film evaporator. 21. The method according to claim 19 or 20,
Wherein said drying zone comprises at least two drying appliances in series and said second appliance is a rotary kiln dryer. The method according to any one of claims 1 to 21,
A fractionating column is used to separate the heavy oil from the solvent in the filtrate stream. The method according to any one of claims 16 to 22,
The heavy oil separation system, characterized in that the filter membrane is made of a material selected from the group of metals, polymers, ceramics and nanomaterials. The method according to any one of claims 16 to 23, wherein
The heavy oil separation system, characterized in that the filtration membrane is composed of a metal selected from stainless steel, titanium, bronze, aluminum, nickel, copper and alloys thereof. The method of claim 23 or 24,
A heavy oil separation system, wherein the membrane is coated with an inorganic metal oxide coating. The method according to any one of claims 1 to 25,
Heavy oil separation system, characterized in that the solvent is selected from toluene, xylene, light cycle oil, medium cycle oil, propane, diesel, benzene, kerosene, catalytic reforming oil, light naphtha, heavy naphtha and mixtures thereof. The method according to any one of claims 1 to 26,
A heavy oil separation system, characterized in that the volume ratio of said feed stream comprising catalyst particles in heavy oil to said solvent in said filtration assembly is in the range of 0.10 / 1 to 100/1. a cleaning solution comprising (a) a stream comprising a mixture of catalyst particles and from 50 to 90% by weight of hydrocarbons and (b) an amount of at least surfactant sufficient to dissolve and remove at least 90% of the hydrocarbons from the catalyst particles A container operable to mix the mixture; And
Means for separating the catalyst particles from the cleaning solution comprising dissolved hydrocarbons,
A system for separating hydrocarbons and heavy oils, including solvents, from catalyst particles, wherein the surfactant is selected from anionic, nonionic, zwitterionic, acidic, basic, amphoteric, enzymatic and water soluble cationic detergents and mixtures thereof. . The method of claim 28,
The surfactant in the cleaning solution is produced in situ by adding at least one alkali metal compound to the stream comprising a mixture of catalyst particles in a hydrocarbon. The method of claim 28 or 29,
And an ultrasonic bath capable of providing ultrasonic waves having a frequency of at least 20 kHz to remove the hydrocarbons from the catalyst particles. The method according to any one of claims 28 to 30,
And a sedimentation tank for separating the catalyst particles from the rinse solution comprising dissolved hydrocarbons. The method according to any one of claims 28 to 31,
Heavy oil separation system, characterized in that the cleaning solution has a surfactant concentration of 0.01 to 10% by weight. 33. The method according to any one of claims 28 to 32,
And at least one drying mechanism for volatilizing hydrocarbons from said catalyst particles. The method according to any one of claims 28 to 33, wherein
The drying apparatus is indirect ignition kiln, indirect ignition rotary kiln, indirect ignition dryer, indirect ignition rotary dryer, electric heating kiln, electric heating rotary kiln, microwave heating kiln, microwave heating rotary kiln, decompression dryer, thin film dryer, flexicoker, fluidized bed A heavy oil separation system, characterized in that it is selected from a dryer, shaft kiln dryer, thin film evaporator, wiped film dryer and wiped film evaporator. A container for receiving a stream comprising a mixture of catalyst particles and 50 to 90 weight percent hydrocarbons;
A plasma system for heating said mixture of catalyst particles and hydrocarbons to a temperature sufficient to volatilize and remove at least 90% of said hydrocarbons from said catalyst particles; And
A system for separating heavy oils from hydrocarbons, including solvents, from catalyst particles, comprising means for collecting volatilized hydrocarbons. 36. The method of claim 35 wherein
And the means for collecting the volatilized hydrocarbon is one of a condenser and a fractionation column. The method of claim 35 or 36,
And the plasma system is capable of heating the mixture of catalyst particles and hydrocarbons to a temperature of 400 to 900 ° C. The method according to any one of claims 28 to 37,
And the catalyst is recovered as a dry powder containing less than 0.5% by weight hydrocarbon. The method according to any one of claims 1 to 38,
Heavy oil separation system, characterized in that the catalyst particles have an average particle size of 1 to 20 microns. The method according to any one of claims 1 to 39,
A heavy oil separation system, wherein the catalyst particles have an average particle size of less than 10 microns. Providing a stream comprising catalyst particulates and from 50 to 90 weight percent hydrocarbons;
Providing a cleaning solution comprising at least a surfactant in an amount sufficient to remove at least 90% of the hydrocarbons from the catalyst particulates;
Mixing the cleaning solution with the stream comprising catalyst particles and hydrocarbons for a sufficient time to dissolve at least 90% of the hydrocarbons in the cleaning solution; And
Separating the cleaning solution comprising the dissolved hydrocarbons from the catalyst particulates, wherein the hydrocarbon comprising heavy solvent and the heavy oil are separated from the catalyst particulates. The method of claim 41, wherein
At least an alkali metal compound is added to the stream comprising catalyst particulates and hydrocarbons such that the cleaning solution is produced in situ. The method of claim 41, wherein
Wherein said surfactant is selected from anionic, nonionic, zwitterionic, acidic, basic, amphoteric, enzymatic and water soluble cationic detergents and mixtures thereof. The method of claim 43,
The heavy oil separation method, characterized in that the surfactant is an anionic detergent. The method of claim 44,
And wherein said surfactant is selected from the group of alkali metal salts, ammonium metal salts, alkanolammonium salts, and mixtures thereof. The method of claim 45,
A process for separating heavy oil, characterized in that the surfactant consists essentially of sodium alkylaryl sulfonates, alcohol sulfates, phosphates and carbonates. The method according to any one of claims 41 to 46,
And wherein said surfactant has a concentration of from 0.001% to saturation in said cleaning solution. The method according to any one of claims 41 to 48,
And the surfactant has a concentration of 0.01 to 10% by weight in the cleaning solution. The method according to any one of claims 41 to 48,
The process of mixing heavy oil, wherein the mixing of the rinse solution with the stream comprising catalyst particulates and hydrocarbons takes place for at least 5 minutes. The method according to any one of claims 41 to 49,
And wherein said cleaning solution comprising dissolved hydrocarbons is separated from said catalyst particulates by decantation. The method according to any one of claims 41 to 50,
And the cleaning solution comprising dissolved hydrocarbons is separated from the catalyst particulates using a settling tank. The method of claim 41, wherein
And treating said mixture of said cleaning solution and said stream comprising catalyst particulates and hydrocarbons by ultrasonication with a frequency of at least 20 kHz. Providing a stream comprising a mixture of catalyst particulates and from 50 to 90 weight percent hydrocarbons;
Treating said mixture of catalyst particulates and hydrocarbons with a plasma source, wherein said mixture of catalyst particulates and hydrocarbons is heated to a temperature of 400 to 900 ° C. for a sufficient time to volatilize said hydrocarbons and produce offgas;
Removing said exhaust gas containing hydrocarbons; And
Collecting the catalyst particulates as a dry powder containing less than 0.5% by weight of hydrocarbons. (a) providing a feed stream comprising a mixture of 5-40 wt% catalyst particles in heavy oil;
(b) adding a sufficient amount of solvent to the catalyst particle mixture in the heavy oil to reduce the heavy oil concentration by at least 40%, thereby removing the mixture from (a) a top phase comprising a portion of the heavy oil and a solvent; (b) separating into two phases of a bottom phase comprising a catalyst oil, a portion of the solvent, a heavy oil concentration lower than an initial heavy oil concentration in the feed stream;
(c) recovering the bottoms phase comprising catalyst particles in a solvent and having a reduced heavy oil concentration. The method of claim 54,
Repeating steps (b) and (c) at least twice to remove at least 90% of the heavy oil from the catalyst particles. The method of claim 54 or 55,
Passing the recovered bottom phase comprising catalyst particles in a solvent and having a reduced heavy oil concentration through a filtration assembly, wherein the filtration assembly is at least 90% of the reduced heavy oil concentration from the recovered bottom phase. And remove the recovered bottoms.
(a) a filtrate stream comprising a solvent and heavy oil removed; And
and (b) a plurality of filtration units for separating the catalyst particles having a further reduced heavy oil content into a retentate stream comprising a portion of said solvent. The method of claim 56, wherein
Collecting the filtrate stream from the filtration assembly and separating the heavy oil from the solvent;
Collecting the retentate stream; And
Recovering catalyst particles from the retentate stream as a dry powder containing less than 1% by weight of heavy oil and a solvent. Passing the feed stream comprising solvent and catalyst particulates in heavy oil through a filtration assembly, wherein the filtration assembly removes at least 90% of the heavy oil from the catalyst particulates and (a) the solvent and the A plurality of filtration units for separating into a filtrate stream comprising heavy oil removed and (b) a catalyst particulate having a reduced heavy oil content and a retentate stream comprising a portion of said solvent;
Collecting the filtrate stream from the filtration assembly and separating the heavy oil from the solvent;
Collecting the retentate stream; And
Recovering catalyst particulates from the retentate stream as dry powders containing less than 1% by weight heavy oil and solvent, from the catalyst particulates in the feed stream comprising 5-40% by weight catalyst particulates in heavy oil. How to separate. Passing the feed stream comprising solvent and catalyst particles in heavy oil through a filtration assembly comprising a plurality of filtration units;
At least one of the filtration units is subjected to dynamic filtration of shear force of at least about 20,000 / sec to have a filtrate stream containing at least 90% of the heavy oil in the feed stream and a heavy oil concentration lower than the heavy oil concentration in the feed stream. A process for separating heavy oil from catalyst particles in a feed stream comprising 5-40% by weight of catalyst particles in heavy oil, comprising producing a retentate stream. Passing a mixture of said feed stream comprising catalyst particles in a solvent and heavy oil through a filtration settling assembly,
The filtration sedimentation assembly has a plurality of channels arranged in parallel, and at least one filtration membrane having an inclination angle of at least 45 degrees from a horizontal plane, wherein the membrane comprises (a) at least one of the solvent and the heavy oil in the feed stream. Having an average pore size selected for separation into a filtrate stream comprising 50% and (b) a catalyst particle having a reduced heavy oil content and a retentate stream comprising a portion of said solvent; And
A process for separating heavy oil from catalyst particles in a feed stream comprising 5-40% by weight of catalyst particles in heavy oil, comprising a receiving chamber for receiving the retentate stream. 61. The method of any of claims 58-60,
The retentate stream is passed through a drying zone to volatilize the heavy oil and solvent to recover the catalyst particles as a dry powder containing less than 1% by weight heavy oil and solvent,
The drying zone may include an indirect fired kiln, an indirect fired rotary kiln, an indirect fired dryer, an indirect fired rotary dryer, an electric heating kiln, an electric heating rotary kiln, a microwave heating kiln, a microwave heating rotary kiln, a decompression dryer, a thin film dryer, a flexicoker, a fluidized bed. At least one drying mechanism selected from a dryer, a shaft kiln dryer, a thin film evaporator, a wiped film dryer and a wiped film evaporator. 62. The method of any of claims 58-61,
And wherein said drying zone comprises at least two drying appliances in series and said second appliance is a rotary kiln dryer. 63. The method of any of claims 58-62,
A fractionation column is used for separating the heavy oil from the solvent in the filtrate stream. Providing a stream comprising a catalyst particle and a mixture of 50 to 90 weight percent hydrocarbons;
Passing said stream comprising catalyst particles and hydrocarbons to a drying zone comprising at least two drying devices of a first drying device and a second drying device, wherein said second drying device is adapted to remove at least 90 hydrocarbons from said catalyst particles. Operated at a temperature high enough to remove the%;
Removing the catalyst from the drying zone as a dry powder, the hydrocarbon comprising heavy solvent and heavy oil from the catalyst particles. 65. The method of claim 64,
And wherein said second drying mechanism is used to remove surface active hydrocarbons bound on said catalyst particles. 66. The method of claim 65,
And the surface active hydrocarbon bound to the catalyst particles is a carboxylate. 67. The method of claim 66,
And a second drying mechanism is a rotary kiln dryer. 68. The method of claim 67,
The rotary kiln dryer is operated at a temperature of 700 to 1200 ° F heavy oil separation method. The method of claim 68,
And the rotary kiln dryer is operated at a temperature high enough to volatilize the carboxylate and reduce the hydrocarbon in the catalyst particles to less than 0.5% by weight. 65. The method of claim 64,
The first drying apparatus is an indirect fired kiln, an indirect fired rotary kiln, an indirect fired dryer, an indirect fired rotary dryer, an electric heating kiln, an electric heating rotary kiln, a microwave heating kiln, a microwave heating rotary kiln, a reduced pressure dryer, a thin film dryer, a flexicoker And a fluidized bed dryer, a shaft kiln dryer, a thin film evaporator, a wiped film dryer and a wiped film evaporator. The method according to any one of claims 64 to 70,
And the first drying mechanism is a thin film dryer having a combined design of the first vertical section and the second horizontal section. The method of claim 10,
Wherein the vertical section operates at a temperature of 200 to 450 ° F. and the horizontal section operates at a temperature of 50 to 100 ° F. 18. Preparing a catalyst slurry comprising catalyst particles in a hydrocarbon oil diluent, wherein the catalyst particles have an average particle size in the range of 1-20 microns and the catalyst is a bulk Group VIB metal sulfide catalyst enhanced with at least Group VIII metals -;
Reacting the heavy oil feedstock with the catalyst slurry in the presence of a hydrogen containing gas to convert the heavy oil feedstock into an improved product, and a mixture of the improved product, the slurry catalyst, the hydrogen containing gas and the unconverted heavy oil feedstock. Generating;
Passing a mixture of the improved product, the slurry catalyst, the hydrogenous gas and the unconverted heavy oil feedstock through a separation zone to separate the gas and the improved product from the slurry catalyst and the heavy oil feedstock;
Separating the heavy oil feedstock from the catalyst particles in the slurry catalyst using a filtration assembly, wherein the filtration assembly has a plurality of filtration units for removing at least 90% of the heavy oil feedstock from the catalyst particles. ;
Recovering the catalyst as a dry powder having less than 0.5% by weight hydrocarbons;
Recovering the Group VIB and Group VIII metals from the recovered catalyst powder;
Circulating the Group VIB and Group VIII metals for use in preparing the catalyst in a catalytic synthesis unit, wherein the heavy oil feedstock is improved to produce a lower boiling hydrocarbon product.

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