RU2134286C1 - Crude hydrocarbon material hydrofining method (versions) and catalyst - Google Patents

Abstract

FIELD: petroleum processing. SUBSTANCE: hydrocarbon material is passed in upward direction reaction zone of hydrogenation converter containing essentially compacted catalyst bed. Distinguishing feature consists in that catalyst in reaction zone is composed of particles with average size ranging from 35 to 3 mesh and such size distribution that at least 90% of catalyst particles have diameter between R₁ (ca.0.04 to 0.63 cm) and R₂ (ca.0.04 to 0.63 cm) provided that R₂/R₁ ratio varies approximately from 1.0 to 1.4. EFFECT: enabled additional control of flow through catalyst bed. 21 cl, 9 dwg

Description

1. Field of invention
The present invention relates to a catalyst and to the replacement of a catalyst operating in a hydrotreatment process for a hydrocarbon feed stream. In particular, this invention relates to a catalyst, method and device for the economical use of the space inside the hydrotreating apparatus in a wide range of processing speeds, without significant fluidization or “boiling” of the packed catalyst bed at high countercurrent rates of hydrocarbon feedstock and hydrogen-containing gas through the packed bed while maintaining continuous or periodic replacement of the catalyst from the apparatus during the "piston" flow around the layer.

2. Description of the prior art
Hydrotreating or hydrogenation treatment to remove unwanted components from hydrocarbon streams is a well-known method for catalytic treatment of such heavy hydrocarbons to increase their commercial value. "Heavy" fractions of liquid hydrocarbons and, in particular, stripped crude oils, oil residues, tar sands, shale oil or liquefied coal, or regenerated oil, usually contain impurity products such as sulfur and / or nitrogen-containing compounds, metals and organometallic compounds, which lead to deactivation of the catalyst particles in contact with these feed fractions and hydrogen under hydrotreatment conditions. Typically, these hydrotreating conditions are: a temperature in the range of 212 to 1200 ^° F (100 to 650 ^° C) and a pressure of 20 to 300 atmospheres. Typically, such hydrotreating is carried out in the presence of a catalyst containing Group VI or VIII metals, such as platinum, molybdenum, tungsten, nickel, cobalt, etc., in combination with various other metal elements, particles of aluminum oxide, silicon dioxide, magnesium oxide, etc. p., which have a high surface to volume ratio. More specifically, the catalysts used for hydrogenation removal of metals, hydrodesulfurization, hydrodetriding, hydrocracking and other heavy oils and the like, are usually made on the basis of a carrier or base material such as alumina, silica, aluminosilicate or possibly crystalline aluminosilicate, with one or more promoter (s) or catalytically active metal (s) (or substances) with the addition of trace materials. Typical catalytically active metals used include cobalt, nickel and tungsten; however, other metals or substances may be selected depending on the application.

 US Pat. No. 5,076,908, issued to Stangeland et al., Proposes a system in which piston flow through a catalyst bed is maintained over a wide range of flow rates of hydrocarbon feedstocks and hydrogen-containing gas through a volume of substantially densified catalyst bed. With such a flow through a densified catalyst bed, a substantially maximum catalyst volume and density is maintained within a predetermined design volume of the apparatus by adjusting the size, shape and density of the catalyst so that the layer does not substantially expand at the estimated rate of liquid flow through this layer. The appropriate particle size, shape and density are determined by selecting the coefficients obtained from an extensive experimental study of layer expansion in a large pilot plant with hydrocarbons, hydrogen and a catalyst at calculated pressure and flow rates, as described specifically below.

 In order to further control such a flow through the catalyst bed, its level inside the reactor is continuously measured, for example, by absorption of gamma radiation, in order to ensure that slight boiling of the catalyst occurs. This regulation is additionally facilitated by the uniform distribution of both hydrogen and liquid feedstock over the entire length of the layer due to the concentric distribution of components - hydrogen-containing gas and liquid hydrocarbon feedstock in other concentric annular passages across the full horizontal cross section of the reactor at their entry into the catalyst layer. In addition, it is desirable that hydrogen is again uniformly distributed and, if necessary, added through a quenching system at one or more intermediate levels along the length of the catalyst layer. Aligning the flows of hydrogen and liquid across a full horizontal section along the length of the layer filled with particles prevents local turbulence and undesirable vertical separation of lighter particles from heavier particles passing through the reactor by a piston stream.

SUMMARY OF THE INVENTION
In a preferred embodiment of the present invention, the desired objectives are achieved by providing a catalyst comprising a plurality of particles having an average diameter varying from about 35 to 3 Tyler units (from 0.42 to 6.68 mm); and such a size distribution that at least about 90 weight. % of the catalyst particles have a diameter in the range from R1 to R2, while:
1) R1 has a value in the range of about 1/64 to 1/4 of an inch, (from 0.04 to 0.63 cm)
2) R2 has a value in the range of about 1/64 to 1/4 inch (0.04 to 0.63 cm), and
3) the value of the ratio R1 / R2 varies from about 1.0 to 1.4; and the dimensional ratio (L / D) is less than about 2.0.

 This catalyst can be used in any hydrogenation process. Preferably, the catalyst is intended to produce a substantially densified catalyst bed in a piston flow reactor during hydrotreatment by contacting the substantially densified catalyst bed with an upstream hydrocarbon feed. More specifically, when the catalyst particles are located in the hydrocarbon conversion zone, a substantially densified hydrotreating catalyst layer is formed; moreover, when passing the flow of hydrocarbon feedstock from bottom to top through a substantially densified catalyst bed, when the volume of catalytic particles is discharged from the bottom of the hydrocarbon conversion zone. As used herein, the term “catalyst” includes other particles that interact with a hydrocarbon feed stream, such as sorbents or other solids for contacting a liquid. The catalyst is located in the reaction zone and the hydrocarbon feed stream flows upward through the catalyst for hydrotreating this stream.

 The catalyst particles have such a size distribution that a maximum of about 2.0 wt.% Of the catalyst particles have a diameter less than R1. In addition, these catalyst particles have such a size distribution that a maximum of about 0.4 wt.% Of the catalyst particles have a diameter less than R3, wherein R3 is less than R1 and the ratio R1 / R3 is about 1.4. The catalyst particles have a maximum abradability of about 1% by weight of the catalyst particles having a diameter in the range of R1; and the catalyst particles have a maximum abradability of about 0.4% of the weight of the catalyst particles having a diameter in the range of R3, where R3 is less than R1 and the ratio R1 / R3 is about 1.4.

In one embodiment of the catalyst, it comprises a plurality of particles having an average diameter varying from about 6 to 8 Tyler units (2.36 to 3.33 mm); and a size distribution such that at least about 97 wt.% of the catalyst particles have a diameter in the range from R1 to R2, wherein:
1) R1 has a value of approximately 0.093 inches (0.27 cm),
2) R2 has a value of about 0.131 inches (0.33 cm); and the size ratio is about 1.0; catalyst particles have a maximum dust content of up to about 1% of the weight of particles passing through a sieve of 8 Tyler units (2.36 mm) and up to 0.2% of the weight of particles passing through a sieve of 10 Tyler units (1.65 mm).

In another embodiment, the catalyst comprises a plurality of particles having an average diameter varying from about 10 to 12 Tyler units (up to 1.65 mm); and a size distribution such that at least about 90 wt.% of the catalyst particles have a diameter in the range from R1 to R2, wherein:
1) R1 has a value in the range of about 0.065 inches (0.17 cm),
2) R2 has a value in the range of about 0.078 inches (0.20 cm);
and the size ratio (L / D) is less than about 2.0; and in which the catalyst particles have such a size distribution that a maximum of about 2.0 wt.% of the catalyst particles have a diameter less than R1, and a maximum of about 0.4 wt.% of the catalyst particles have a diameter less than R3, and R3 is less R1 and the ratio of R1 / R3 is about 1.4.

In yet another embodiment, the catalyst for hydrotreating a hydrocarbon feed stream that flows from bottom to top through a hydrogenation conversion reaction zone containing a substantially densified catalyst bed includes a plurality of catalyst particles having an average diameter varying from about 6 to 8 Tyler units (2, 36 to 3.33 mm); and a size distribution such that at least about 90 wt.% of the catalyst particles have a diameter in the range from R1 to R2, wherein:
1) R1 has a value of about 0.093 inches (0.24 cm),
2) R2 has a value of about 0.131 inches (0.33 cm);
and the size ratio (L / D) is less than about 2.0; and in which the catalyst particles have such a size distribution that a maximum of about 2.0 wt.% of the catalyst particles have a diameter less than R1, and a maximum of about 0.4 wt.% of the catalyst particles have a diameter less than R3, and R3 is less R1 and the ratio of R1 / R3 is about 1.4.

In another aspect of the invention, the objectives are also achieved due to the wide representation of the method of obtaining a substantially densified layer of hydrotreating catalyst, moving from top to bottom in a piston mode, inside the hydrogenation transformation reaction zone, this method comprising the steps of:
a) the formation of many ring mixing zones in the hydrogenation reaction zone containing a substantially densified hydrotreating catalyst layer, as described above, each ring mixing zone containing a hydrocarbon feed stream comprising a liquid component and a hydrogen-containing gas component, and in which the ring mixing zones are concentric in relation to each other and coaxial in relation to the reaction zone of the hydrogenation transformation;
b) withdrawing the hydrocarbon feed stream from each annular mixing zone of step (a) into a substantially densified hydrotreating catalyst bed so that the hydrocarbon feed flow rises from each annular mixing zone through the substantially densified catalyst bed;
c) removing the volume of catalyst particles from the hydrogenation conversion reaction zone in order to obtain a substantially densified hydrotreating catalyst bed moving downward by the piston stream within the hydrogenation conversion reaction zone.

 This method may further include injecting a quenching agent (e.g., quenching liquid) into a substantially densified hydrotreating catalyst bed. This injection includes passing the quenching material through a first passage zone having a first passage diameter; passing the quenching material from the first passage zone to the second passage zone having a second passage diameter that is larger than the diameter of the first passage zone; passing the quenching material from the second passage zone to the third passage zone having a third passage diameter that is less than the diameter of the second passage zone; passing the quenching substance from the third passage zone into the catalyst bed located in the reaction zone of the hydrogenation conversion, through which a stream of hydrocarbon feed passes.

 The substantially densified hydrotreating catalyst bed is located in the reaction zone within the reactor volume so that the substantially densified hydrotreating catalyst bed occupies a maximum of the reactor space. This substantially densified catalyst bed occupies at least about 50% of the reactor volume; preferably at least about 60% of the volume; and more preferably at least about 65 to 70% of the reactor volume.

 From the foregoing, it becomes apparent that the achievement of the desired objectives of the present invention is directly affected by several significant factors that also contribute to the efficient use of the reactor volume of this process in order to ensure the piston flow of catalyst particles in the reactor without boiling, while maintaining contact with a countercurrent flow of hydrocarbons, including gas and liquid, at maximum space velocity. Such significant factors are: i) the size, volume, and density characteristics of such catalyst particles at preselected flow rates and hydrocarbon feed pressure; ii) control the boiling and / or soaking of the catalyst layer during the movement of a liquid stream of hydrocarbon feedstock and hydrogen; iii) the laminar flow of catalyst particles upon entry into (and from) the moving catalyst bed to replace (or regenerate, or renew) without boiling or melting the bed; iv) a concentric uniform ring feed of alternating rings of gaseous and liquid components of hydrocarbon feed into a fully moving catalyst bed that is able to quickly recover from a drop or change in pressure in the reaction vessel in order to resume supply of alternating rings of gaseous and liquid components throughout the run (for example, over several thousand hours); and v) redistributing the gaseous components along the axis of the moving layer.

Brief Description of the Drawings
FIG. 1 is a partial cross-sectional view representing a catalyst bed with a plurality of overlapping layers prior to the start of the piston flow;
FIG. 2 is a partial cross-sectional view representing a catalyst bed that moves downward in a piston flow mode;
FIG. 3 is a bottom view of concentric and radial catalyst bed support means for a truncated conical or pyramidal mesh filter;
FIG. 3A is a partial cross-sectional view of a reactor and a partial perspective of another embodiment of a catalyst support means;
FIG. 4 is a partial cross-sectional view of the reactor and catalyst support means of FIG. 3A, which comprise a plurality of annular mixing zones under a substantially densified hydrotreating catalyst bed, each annular mixing zone containing a liquid hydrocarbon component and a hydrogen-containing gas component, and in which the annular mixing zones are concentric with respect to each other and coaxial with respect to the reactor and substantially densified catalyst layer hydrotreating;
FIG. 5 is a partial cross-sectional view of a reactor and support means of FIG. 4 with inert tablets and shows ribs or knitting needles attached to a non-perforated central plate and supporting a plurality of segmented plates;
FIG. 6 is a partial cross-sectional view of the reactor and support means of FIG. 5 with inert tablets around which a liquid hydrocarbon component and a hydrogen-containing gas component pass before entering the mixing ring zones;
FIG. 7 is a horizontal cross-sectional view of a hydrotreating vessel or reactor, representing, in an upper planar view, a quenching system (s) or device for distributing a quenching agent (e.g., quenching liquid or gas) into a catalyst bed at a desired layer level;
FIG. 8 is a partial vertical sectional view taken in the direction of the arrows and along the plane of line 8-8 in FIG. 7;
FIG. 8A is a partial cross-sectional view of a nozzle mounted on a side surface of a quenching pipe;
FIG. 9 is a partial vertical sectional view taken in the direction of the arrows and along the plane of line 9-9 in FIG. 7.

Detailed description of the invention, including preferred embodiments of the invention
Let us now consider in detail the drawings, first more specifically FIG. 1, which shows a hydrotreating system embodying the method of the present invention to substantially increase both the duration of the catalytic activity of the entire volume or layer of catalyst 10, and the efficiency of using a separate reactor of a given reaction volume, such as reactor 11. The reactor 11, as shown by the thickness of its lateral cylindrical walls 12 and domed body covers or ends 13 and 14, is designed to interact with a hydrogen-containing gas mixed with a liquid hydrocarbon stream at to about 300 atmospheres and a temperature of about 650 ^o C. Such a flow of reactant gas stream and a liquid hydrocarbon feedstock is preferably mixed and introduced as a single stream through bottom cover 13 via line 16.

 In order to maximize the benefits of catalytic hydrotreating a stream of hydrocarbon feedstock and hydrogen-containing gas, it is essential that the reactor 11 contains as much catalyst as possible within the calculated volume of the tank 11. Accordingly, as indicated, the means 17 for maintaining the catalyst layer 10 is located in the reactor 11 as low as possible at the same time, a complete and appropriate dispersion of the hydrogen phase within the liquid hydrocarbon stream is ensured. At the same time, the upper boundary of the layer 10 is close to the upper domed cover 14, while an appropriate space 21 is provided for separating the entrained catalyst from the resulting products, which are discharged from the central pipe 18. To ensure that the catalyst is not drawn into the liquid products, exiting the central pipe 18, a screen can be mounted in the space 21 above the surface of the layer 20, which defines the top of the catalyst layer 10. Then, fresh the catalyst through a tube 19 passing through the filter 15. It is desirable that the upper level or top of the catalyst layer 10, designated as the surface of the layer 20, is preferably continuously monitored by measuring the absorption of gamma radiation, which is possible by placing a source and a gamma radiation detector (in the drawings not shown) in the immediate vicinity of the surface of the catalyst layer 20. Such a gamma radiation source may be in the form of radioactive isotopes, such as cesium-137, located inside the reactor in pockets of a special design. Alternatively, the source may be an electrically adjustable source, such as a gamma radiation generator activated by thermal neutrons. The detectors can take the form of an ionization tube, a Geiger-Muller counter, or a scintillation detector. Suitable sources and detectors are manufactured by Ronan Engineering Co., Texas Newclear and other suppliers. By determining the level of the surface 20 in accordance with the invention, it is possible to maintain the catalytic material at an optimum level so that the reactor is never overfilled.

 Overflowing the reactor increases the risk that the catalyst particles will crush in the shut-off valves of the conveyor lines when they close at the end of each movement of the catalyst particles. In addition, control of the level of the layer is necessary in order to ensure that boiling of the layer is minimized and that unwanted deviations from the design flow rate for hydrogen and hydrocarbon feed from bottom to top through layer 10 are eliminated for the selected catalyst. To this end, size, shape and the density of the catalyst particles supplied to the bed is selected in accordance with the design maximum flow rate of the feed streams in order to prevent such boiling. This control ensures that the bed 10 sequentially moves downward inside the reactor in a reciprocating flow mode. The piston flow of the catalyst bed 10 is illustrated in FIG. 1 and 2 and it can best be described in such a way that when the lowest volume layer A is removed, the next volume layer B extends down to occupy the lowest volume part B. The removed lowermost volume layer A is replaced by the upper volume layer J. This the procedure is repeated again (as best shown by the dashed lines in Fig. 2) by removing the lowest volumetric layer B, which causes the next volumetric layer C to flow downward in the piston mode to occupy the lowest volumetric part B. The removed lowest the volumetric layer B is replaced by the upper volumetric layer K. This procedure can be continuously repeated to determine the piston movement of the catalyst layer 10 downward in the direction of the arrow W in FIG. 2.

 The methodology for determining whether the flow of catalyst layer 10 is piston can be any suitable technique. For example, in a preferred embodiment of the present invention, in which metals (e.g., vanadium) are removed from the hydrocarbon feed stream, the catalyst bed 10 moves like a piston if, when analyzing a catalyst sample (e.g., 15 catalyst particles) from the recovered stream, it is found that according to elemental analysis, this sample has a uniformly high metal content, preferably at least 1.5 times greater than the average metal content in the catalyst layer 10, and more preferably at least re 2.0 times greater than the average metal content in the catalyst layer 10. Those of ordinary skill in the art will be able to determine the average amount of catalyst in the layer 10 from the data of the total metal content removed from the hydrocarbon stream, the weight of the catalyst layer 10, etc. .

 It should be understood that when using or mentioning in the description or claims of any type of movement of the catalyst or catalyst layer 10 (for example, "removal, movement, supply, replacement, transfer, flow, flow, transfer, transfer, addition, addition, mixing" and etc.) for any type or mixture of catalyst without approving or mentioning the base, the main one for such movement of the catalyst or catalyst layer may be any type of method, such as “intermittently”, “periodically”, continuously, floor in a continuous manner, etc. Thus, only as an example, the removal of the lowest volumes of the layers and the addition of the upper bulk layers can be done in a periodic manner, in a continuous manner or even in a one-time manner, and in all cases without affecting the essence and scope of the present invention. It should also be understood that the removal or removal of the catalyst and the addition or replacement of the catalyst are mutually exclusive and can be carried out simultaneously or at different times without affecting the essence and scope of the present invention. Preferably, the addition or replacement of the catalyst is carried out after removal or removal of the catalyst and after moving the catalyst layer 10 down to a stationary state or a fixed position.

 To further ensure that the piston flow extends along the entire length of the layer, and especially in the bottom, the means for supporting the layer 17 are specially characterized by the configuration of a truncated polyhedron or cone.

 As shown in preferred embodiments of FIG. 3-6, the carrier 17 includes a series of annular polyhedra approaching in shape to rings that are formed from a plurality of segmented plates 27 (see FIG. 3) between radial ribs or spokes 26 extending from the non-perforated central plate 25 to the side wall 12 of reactor 11 As shown in FIG. 3 and 5, the spokes 26 may be of any suitable geometric shape, such as a rod (see FIG. 5) or a substantially flat plate (see FIG. 3), which divide the periphery of the reactor into many segments (in this case eight) and similarly support the ends of the outer octahedral ring 23 of the support means 17 formed by annular or peripheral plates 27. In each case, the radial ribs or knitting needles 26 and the annular segmented plates 27 form a plurality of concentric rings or annular polyhedra that support a conical or pyramidal perforated plate or filter 28 is formed. Thus, the filter 28 is permeable to both gas and liquid, which rise from the bottom of the vessel 11.

 In one preferred embodiment of the invention, the specific design of the concentric annular polyhedra, which are shown in FIG. 3, the interconnected plates 27 form a plurality of ring-like structures, usually axially protruding parallel to the side wall 12, with the radial ribs or spokes 26 radially protruding toward the side wall 12 of the reactor 11. A mixture of a stream of hydrocarbon feedstock and a hydrogen-containing gas that will enter the catalyst bed 10, is divided by gravity into radially alternating rings of liquid and gas, composed of adjacent segments between each pair of radial spokes 26. Thus, both phases flow up h Through alternating concentric annular passages under the filter 28. The preferred gas-liquid separation in each ring includes an upper gas segment overlapping an adjacent lower liquid-filled annular segment. Therefore, both flows have equal (and with an adjacent angle) access to the layer through the filter 28. A lot of alternating rings of hydrogen-containing gas and hydrocarbon liquid provide a uniform and equal flow of both phases along the entire cross section of the filter 28 into layer 10. Among other factors, we specifically found that this configuration provides uniform and equal distribution over the entire cross section of the catalyst bed. This uniform distribution over the entire diameter of the layer 10 provides a sector of calm flow, which is formed directly above the Central plate 25, which truncates the conical means 17 for maintaining the layer. This significantly reduces the possible local boiling or turbulent flows that can be caused in the catalyst bed at the catalyst removal point through the inlet 30 of the inverted J-shaped tube 29 to provide a localized laminar flow of catalyst and liquid into (and from) the layer 10.

 The uniform flow of the mixture of the hydrocarbon feed stream and hydrogen is specifically facilitated on the inlet side of the plates 27 of the support means 17 through the inlet of the increased pressure 33 located between the carrier 17 and the circular plate element 31, which protrudes across the full cross section of the reactor 11. This round plate element 31 defines a lattice structure supporting a permeable filter 6 having one or more openings, as best shown in FIG. 4, 5 and 6. As further shown in FIG. 4, 5 and 6, a permeable filter 6 supports a layer 3 of a plurality of inert tablets 4 (eg, aluminum oxide tablets) that are sized so as not to pass through openings in the permeable filter 6 in order to prevent turbulent flows in the pressure chamber 33 and in order to retain bubbles of a hydrogen-containing gas diffused into the hydrocarbon feed stream. The plate 31 includes many similar pipes of large diameters 32, forming holes in the plate 31.

 Each pipe has a diameter of several inches and extends axially to a similar depth of about 4-6 inches (10-15 cm), below plate 31. Pipe 32 provides equal access to the mixture of hydrogen and hydrocarbon feed in the pressure chamber 33. Uniform distribution of the incoming feed stream into the bottom cover 35 of the feed line 16 can also be promoted by a reflection plate 34 (see FIGS. 1 and 2) to ensure uniform distribution of excessively large hydrogen bubbles that may be contained in the feed stream over the cross section the plate 31 and the uniform distribution to each pipe 32 for flow into the pressure chamber 33. The length of the pipes 32 can be selected so that a suitable gas cushion is formed under the plate 31 to suppress unrest in the feed streams entering the manifold 35.

 As noted above, the vertical transverse width or axial length of the plates 27, which define each individual annular and radial segments, provides equal access for hydrogen and liquid feed to the catalyst layer 10 and passes under the filter 28 so that they effectively form gaseous and hydrocarbon rings raw materials that alternately cross the full diameter at the inlet side of the catalyst layer 10. Thus, no single entry zone into the catalyst layer 10 becomes highlighted or preferred Noah for the flow of either liquid or gas. In addition, if pressure disturbances lead to the complete wetting of the filter 28 by the liquid phase, gas evolution is facilitated by the width of the area of each segment between the plates 27 and the radial plates 26.

 In another preferred embodiment of the specific design of the concentric annular polyhedra, which is illustrated in FIG. 3-6, the liquid hydrocarbon component LH and the hydrogen-containing gas component HG (hydrogen-containing gas bubbles) entering the LH-HG mixture into the pressure chamber 33 from the pipes 32 are visible. The LH-HG mixture is introduced into the pressure chamber. In this preferred embodiment of the present invention, the annular or peripheral plates 27 are attached to and supported by radial ribs or spokes 26, each of which has a vertical or transverse width that is substantially equal to the vertical or transverse width of the annular or peripheral plates 27. The radial ribs or knitting needles 26 also act as a means of reducing the size of the bubbles of the hydrogen-containing gas, especially the very large bubbles of the hydrogen-containing gas from the gas component HG. Those skilled in the art will readily agree that the number of radial ribs or spokes 26 used will depend on a number of factors, such as the expected number of very large hydrogen-containing gas bubbles in the hydrocarbon stream flowing from the bottom up, the weight of the catalyst layer 10, etc. Interconnected plates 27 and the radial ribs or spokes 26 form a network or mesh structure defining a plurality of annular mixing zones, generally indicated in FIG. 3-6 as MZ. These annular MZ mixing zones are substantially continuous or usually infinite MZ zones and can contain or can be subdivided into any reasonable desired number of mixing zones (or pre-mixing zones), such as MZ1, MZ2, MZ3, MZ4, MZ5 and MZ6 in FIG. 4 and 5. Each of the individual mixing zones MZ1, MZ2, MZ3, MZ4, MZ5 and MZ6, designed for all practical purposes, is an annular continuous or infinite mixing zone of uniform thickness, with the exception of periodic interruption by radial ribs 26, which are relatively narrow oppositely located ribs distributed between any pair of adjacent ribs 26-26. As is apparent from FIG. 3-6, a non-perforated plate 25, which is preferably located away from the plate 31 and the filter 6 so that inert tablets 4 can rest on the filter 6 and the plate 31, immediately below the non-perforated central plate 25. The mixing zone MZ1 is a substantially cylindrical zone mixing with the open top and the boundaries defined by the space between the set of mutually engaged and paired plates 27 and the perimeter of the non-perforated Central plate 25.

 The plurality of annular mixing zones MZ (or annular continuous or infinite mixing zones MZ2, MZ3, MZ4, MZ5 and MZ6) under the catalyst bed 10 are concentric with respect to each other and coaxial with respect to the reactor vessel 11 and catalyst layer 10. The plates 27 may be located radially from each other plate at any suitable distance (preferably at the same distance) to help achieve the objectives of the present invention. However, preferably, the plates 27 are located radially from each other plate, usually at the same thickness or distance, which varies from about 1 inch (2.54 cm) to 4 feet (122 cm), more preferably from about 6 inches (15 cm) to 3 feet (91 cm), most preferably from about 1 (30.48 cm) to 2 feet (61 cm). The radially located relationship between and among the plates 27 usually defines a uniform thickness for each annular mixing zone (i.e., MZ2, MZ3, etc.). It should be understood that although the plurality of annular mixing zones MZ are shown in FIG. 3-6, as a plurality of zones of non-circular geometric shape (for example, octagonal in FIG. 3), it is an object and scope of the present invention that the plurality of annular mixing zones MZ may consist of zones of any geometric shape, including not only octagonal zones, but there are also many concentric circular mixing zones and the like, which all can also be concentric with respect to each other and coaxial with respect to the reactor 11 and / or the catalyst layer 10 (or the reaction zone of the hydrogenation transformation).

Consequently, the plates 27 provide for the formation of strips, usually of the same thickness and substantially concentrically round, of hydrocarbon feedstocks, which are also coaxial with respect to the catalyst layer 10. For the purpose of example only, as best seen from FIG. 3-6, annular mixing zones MZ2, which are limited by eight mutually engaged or paired plates 27 ₁ and eight mutually engaged or paired plates 27 ₂ . Each of these eight plates 27 ₁ and eight plates 27 ₂ form an annular boundary for a substantially round strip of hydrocarbon feed stream in the mixing zone MZ2. Since the space or distance between the plates 27 ₁ and 27 _{2 is} usually uniform around the periphery, the thickness or size of the substantially round strip of the hydrocarbon feed stream in the mixing zone MZ2 is substantially uniform in the cross section and / or equal in the cross or horizontal section. Similarly, the MZ6 mixing zone is made up of eight mutually engaged or paired plates 27 ₅ and eight mutually engaged or paired plates 27 ₆ , which in combination form annular boundaries for substantially circular streaks of hydrocarbon feed stream in the MZ6 mixing zone. As previously indicated for the plates 27 ₁ and 27 ₂ , since the space or distance between the plates 27 ₅ and 27 _{6 is} usually uniform along the periphery, the thickness or size of the substantially round strip of the hydrocarbon feed stream in the mixing zone MZ6 is substantially uniform in cross section and / or equal in cross-section or horizontal section. Plates 27 ₂ , 27 ₃ 27 ₄ and 27 _{5 are} likewise functionally mutually engaged or paired to define annular boundaries for the mixing zones MZ3, MZ4 and MZ5.

As best shown in FIG. 1, the ribs 26 extend radially from the non-perforated center plate 25 and visually represent pie-shaped segments in the plane. Between each pair of adjacent ribs 26-26, the length of the respective plates 27 increases from the plate 27 ₁ towards the plate 27 ₆ , while the thicknesses remain substantially the same as best shown in FIG. 3-4. Thus, the plate 27 _{2 is} longer than the plate 27 ₁ , although it has approximately the same width. Similarly, plate 27 _{3 is} longer than plate 27 ₂ , plate 27 _{4 is} longer than plate 27 ₃ , plate 27 _{5 is} longer than plate 27 ₄ , and plate 27 _{6 is} longer than plate 27 ₅ , although at the same time all plates 27 usually have the same width or longitudinal extension below filter 28 (see FIG. 3). Thus, the vertical dimensions or width of the plates 27 (i.e., the structural elongations of the plates 27, which are usually parallel to the longitudinal axis of the reactor 11 and / or the catalyst layer 10 in the reactor) are usually the same. All plates 27 are preferably positioned so that a stream of hydrocarbon feed flows parallel to the longitudinal axis of the catalyst layer 10 before entering and contacting this layer. Both the upper and lower edges of the plates 27 ₁ , 27 ₂ , 27 ₃ , 27 ₄ , 27 ₅ and 26 ₆ all have different levels or heights. MZ mixing zones are different from a plurality of pipes, passages or tubular channels or introducing a substantially complete or integral cylindrical flow of hydrocarbon feed into the catalyst bed 10. As best seen in FIG. 4 and 5, the upper and lower edges of the plates 27 ₁ are at a different level or height than the upper and lower edges of the plates 27 ₂ , which are at a different level or height than the upper and lower edges of the plates 27 ₃ . Similarly, the upper and lower edges of the plates 27 ₃ are at a different level or height than the upper and lower edges of the plates 27 ₄ , which are at a different level or height than the upper and lower edges of the plates 27 ₅ . The upper and lower edges of the plates 27 ₅ are at a different level or height than the upper and lower edges of the plates 27 ⁶ .

 After the LH-HG mixture enters and passes through the filter 6 into the pressure chamber 33, the current LH-HG mixture enters each usually continuous annular mixing zone (MZ2, MZ3, etc.) to split or separate the current LH-HG mixture into the plurality of current typically continuous ring mixtures LH-HG, which are indicated in FIG. 11 as LH-HG2, LH-HG3, LH-HG4, LH-HG5 and LH-HG6. As indicated previously, the mixing zone MZ1 is also mainly a mixing zone of a circular or cylindrical shape, which is limited by the space between the perimeter of the non-perforated central plate 25 and mutually paired segmented plates 27, and receives a stream of hydrocarbon feed (i.e., liquid hydrocarbon feed and / or hydrogen-containing gas) inside and through the space to which it is limited. In a preferred embodiment of the present invention, as best shown in FIG. 6, before the current LH-HG mixture enters each normally continuous ring mixing zone (MZ1, MZ2, MZ3, etc.), the LH-HG mixture passes around a plurality of inert tablets 4 in zigzag directions, which reduces the likelihood of turbulent flows and allows hydrogen gas diffuse from the bubbles into the liquid hydrocarbon and prevents their agglomeration into larger bubbles. The flow of hydrocarbon feed to the mixing zone MZ1 is designated as LH-HG1. Many LH-HG mixtures (i.e., LH-HG1, HL-HG2, etc.) pass through a filter 28 and accordingly enter the catalyst bed 10 from each mixing zone (i.e., MZ1, MZ2, MZ3, etc.) at this flow rate so that the catalyst layer 10 does not boil, flow and expand in the upper direction or in the direction of the filter 15 and the domed cover 14 more than 10% in length beyond the substantially full axial length of the catalyst layer 10 in an ordered state, such as a stationary state the layer shown in FIG. 1. A plurality of typically continuous LH-HG ring mixtures flow upward through a filter 28 into a catalyst layer 10. This catalyst layer 10 of the present invention preferably includes catalyst particles that have substantially the same and / or uniform size, shape and density and which are selected in accordance with the average optimal flow rate of hydrocarbon feed (i.e., a mixture of a liquid hydrocarbon component LH and a hydrogen-containing gas component HG or continuous ring mixtures LH-HG) flowing into the chamber of increased yes 33 and then inward and through a plurality of mixing zones MZ2, MZ3, etc. All flow rates of the plurality of corresponding LH-HG mixtures (i.e., LH-HG 1, LH-HG2, etc.) from the corresponding mixing zones MZ1, MZ2, etc. and then also the flow rates of hydrocarbon feed to the pressure chamber 33 through line 16 are regulated at a level and to such an extent that is sufficient to maintain the expansion or wandering of catalyst layer 10 at a level of less than 10% over the entire length or outside substantially full the axial length of the catalyst layer 10 in a compacted state. More preferably, the expansion of the substantially densified catalyst bed is limited to less than 5%, most preferably to less than 2%, or even less than 1%, over the entire length or outside the substantially full axial length of the catalyst bed 10 in the packed state. Ideally, the expansion of a substantially densified catalyst bed is limited to 0% in length.

 The flow rate of hydrocarbon feedstock over a length of 16 should be at a level that is slightly greater than the optimum flow rate. The optimal speed of the processed liquid flow through a substantially densified catalyst bed will vary for various process plants, depending on several factors, including the characteristics of the hydrocarbon and hydrogen-containing raw materials, technical specifications for the catalyst, process goals, etc. Based on the catalyst particles having almost the same and / or uniform size, shape and density, flow rate of hydrocarbon feeds preferably ranges from about 0.01 feet / s (0.3 cm / s) to 10 ft / s (304.8 cm / s) and more preferably varies from about 0.01 ft / s (0.3 cm / s) to 1.0 ft / s (30.48 cm / s). Similarly and / or in the same way and additionally based on catalyst particles having practically the same and / or uniform size, shape and density, flow rate of continuous ring mixtures LH-HG (i.e. the sum of the flow rates LH-HG1 to LH-HG6 from the zones mixing from MZ1 to MZ2, respectively, in Fig. 4) should be at a level that is slightly higher than the optimal flow rate, which preferably varies from about 0.01 ft / s (0.3 cm / s) to 10 ft / s (304.8 cm / s) and more preferably varies approximately from 0.01 ft / s (0.3 cm / s) to 1.0 ft / s (30.48 cm / s). The specific flow rate will depend, as indicated above, on the number of variables, such as the particular application (for example, metal removal or desulfurization, etc.) of the hydrotreatment process. However, the specific flow rates should be controlled at an acceptable level to the extent that it is sufficient to limit the expansion of the substantially densified catalyst bed to less than 10% over the entire length or outside the substantially densified hydrotreating catalyst bed in a packed state.

 In a preferred embodiment of the invention and for such a flow rate of hydrocarbon feed and such a speed of continuous ring mixtures LH-HG, the catalyst particles preferably have substantially the same and / or uniform size, shape and density in order to provide the desired degree of demetallization or desulfurization of the liquid hydrocarbon the LH component in the hydrocarbon feed stream (i.e., the LH-HG mixture) in the resulting hydrogenated hydrogenated liquid products that are removed from the reactor 11 through a cent pipe 18. At the above flow rates of hydrocarbon feed passing through line 16 and for flow rates of typically continuous ring mixtures LH-HG (i.e., LH-HG1, LH-HG2, etc.), the obtained refined liquid products preferably are discharged through the central pipe 18 from the reactor 11 at speeds varying from about 0.01 ft / s (0.3 cm / s) to 10 ft / s (304.8 cm / s) and more preferably vary from approximately 0.01 ft / s (0.3 cm / s) to 1.0 ft / s (30.48 cm / s). The discharge rates of the obtained enriched liquid products should not be greater than the optimal flow rate, and it will also vary for various process plants depending on several factors, including the characteristics of the hydrocarbon and hydrogen-containing raw materials, technical specifications for the catalyst, process goals, etc. The specific rates of product withdrawal should be controlled at an acceptable level to the extent that is sufficient to prevent and / or limit the expansion of the substantially densified catalyst bed to less than 10% (more preferably less than 5%, most preferably less than 2% or even less than 1 %) along the entire length or outside substantially the entire axial length of the layer 10 in a compacted state.

 The arrangement of the inlet distributor 31 for uniform distribution of the hydrogen-containing gas stream and the hydrocarbon feed stream, as shown in FIG. 4 can be altered by the formation of uniformly distributed cylindrical passages into the pressure chamber 33. A particular advantage of using pipes 32 compared to simple perforations or holes of the corresponding diameter is the formation of a gas cushion under the plate 31 in the areas around the individual pipes 32. The authors found which is desirable, since such a gas cushion held under the tray or plate 31, smooths out pressure disturbances that may arise from changes in flow velocity and a mixture of hydrogen and liquid supplied to the reactor. However, the length of the pipes 32 is kept as short as possible to carry out their functions. And here this is due to the desirability of using the smallest possible reaction space available in the reactor 11 for everything that does not relate to contacting the feed streams with the conversion catalyst. A particular advantage of using pipes 32 over a combination of pipes and perforations is that the projected pattern of flow distribution is maintained over a wider range of flow rates. In the case of pipes and perforations, gas usually leaves the perforations, and liquid exits the pipe. However, the gas flow can find new ways through the pipes if the gas flow increases or the perforations become clogged, which will lead to an unforeseen and potentially undesirable flow pattern.

Turning now to the details of FIG. 7-9, where an embodiment of the quenching system 39 is shown, which not only further contributes to maintaining the piston flow of the catalyst layer 10 along the entire axial length, but also contributes to:
1. The resumption of the movement of the hydrogen-containing gas (ie, the velocity of the hydrogen-containing gas component) in the upper reaction zones of the catalyst layer 10, thereby maintaining and providing predictable conditions for a non-boiling, substantially densified catalyst layer.

 2. Transferring the possibility of intermediate cooling of the reactor or quenching load from the entire process gas quenching medium to the quenching medium selected from the group consisting of quenching gas, quenching liquid and mixtures thereof, or in some cases to the quenching medium completely consisting of technological quenching liquid.

 3. And regulating part of the quenching gas of any combined gas / liquid quenching medium in order to maintain a hydrogen-containing gas balance based on the chemical requirements of the hydrotreating process and not necessarily the complete cooling and / or quenching requirements.

 4. And turning off the initial control of the intermediate cooling and / or quenching of the reactor with a liquid quenching substance or a quenching medium stream, which is automatically supported by a gaseous quenching substance or quenching gas flow in the case when the liquid quenching substance or quenching fluid flow is interrupted for some reason. In this preferred embodiment of the present invention, the quenching system 39 can be used as part of any type of hydrotreating process, including but not limited to hydrotreating in a fixed bed, a boiling or expanding bed, and the like.

 The quenching system 39 for the embodiment of the invention shown in FIG. 7-9 includes a feed unit for the main quenching medium shown generally at 130; and a secondary quenching medium supply unit, shown generally at 132; and attached and / or attached to and connected to the supply unit of the main quenching medium 130 for receiving the quenching medium or substance (i.e., liquid quenching and / or gas quenching) and for distributing it over the catalyst layer 10 in accordance with the methodology, which will explained in detail below. Supporting means, typically shown as 134, are attached and / or attached to the reactor 11 (i.e., to the inner peripheral surface of the reactor 11) and to the supply units of the primary and secondary quenching media 130 and 132 to support these supply units in suspension relative to the bed catalyst 10 and to maintain both blocks 130 and 132 in a general stationary position relative to the reactor 11.

 The supply unit of the main quenching medium 130 preferably includes a main hollow element 138 receiving the quenching medium, which is a pressure line 142 for receiving quenching or quenching medium or means that is transported from a quenching source outside the reactor 11.

 The primary hollow element 138 receiving the quenching medium or pressure line 142 is formed with one, or several, or a plurality of typically hollow transverse elements or transverse pressure lines 150, which normally extend normal from it and are connected to the main hollow element 138 or pressure line 142 for hardening. Many transverse pressure pipelines 150 have a diameter (i.e., inner diameter) less than or narrower than the diameter of the quenching pipe 142. As best shown in FIG. 8, the main hollow member 138 receiving the quenching medium (or quench discharge pipe 142) is also formed with an inlet pressure pipe 146a (or a secondary inlet pipe) that connects to the main hollow member 138 receiving the quenching medium (or with a pressure pipe 142 for quenching) for receiving and passing a quenching medium or substance. The quench pressure inlet pipe 146a has a diameter (i.e., inner diameter) less than or narrower than the quench pressure pipe 142. The diameter of this pipe 142 is larger than the diameter of the quench inlet pressure pipe 146 so that it can receive, or otherwise accept, and maintain a large or sufficient volume of quenching medium for immediate and / or uninterrupted supply to the secondary quenching medium supply unit 132.

 The longitudinal ends or opposite ends of the main hollow element 138 receiving the quenching medium, or the pressure pipe 142 for quenching, have a pair of supports of the guiding type pipe (or primary supports), generally shown as positions 182-182, respectively attached to the support means 134, more specifically to the enclosing member, shown below as 180. The manifold (or primary) supports 182-182 operate so as to connect the main hollow member 138 receiving the quenching medium (or pressure hardening conduit 142), with support means 132. The collector (or primary) supports 182-182 can be made of any suitable material, preferably any thermally expandable material, which can be compatible with metallurgical requirements for the support of the main hollow member 138 receiving the quenching medium (or the quenching pressure pipe 142) is dependently coupled to the support means 132, while at the same time providing some freedom of movement due to thermal expansion.

 The quenching medium supply unit 130 also includes a quenching medium inlet element 140 that passes through the cylindrical side wall 12 of the reactor 11 and is attached and / or attached to the inlet pressure pipe 146a to transfer or pass the quenching medium or substance into the inlet pressure pipe 146a, which this medium, in turn, is transmitted or passes for subsequent transport to the main hollow element 138, receiving the quenching medium (or pressure pipe 142 for quenching). As indicated previously, the quenching medium or material from the quenching source that was previously obtained and placed outside the reactor 11. The quenching medium inlet 140 is preferably an inlet pressure quenching pipe 146 for the quenching medium that has a diameter (i.e., inner diameter) substantially equal to the diameter (i.e., inner diameter) of the pressure inlet pipe 146a. In a preferred embodiment of the present invention, the quench inlet pressure conduit 146 is connected to the inlet pressure conduit 146a by a connection clip (or connection means), generally shown at 158, which acts as a connecting and disconnecting device or element, making it easy to connect or attach the inlet piping 146 for the quenching medium to the inlet pressure pipe 146a and to facilitate the separation of the two inlet pipes 146 and 146a any desired reason, such as cleaning and / or unblocking the inlet conduit 146 and / or 146a, etc. The connection clamp 158 may be any suitable connection means or unit that is capable of connecting, linking and disconnecting any pair of elements or conduits to act as a quenching system 39 of this preferred embodiment of the invention. A suitable connection clamp 158 is a clamp sold by ABC Vetco Gray (Houston, TX) under the registered trademark GRAYLOC. The quenching inlet pressure pipe 146 feeds the main hollow element 138 receiving the quenching medium (i.e., the quenching pressure pipe 142 and its associated inlet pressure pipe 146a) at a location that is usually coaxial with respect to the longitudinal axis of the reactor 11 and / or catalyst bed 10.

 The secondary quenching medium supply unit 132 includes one or more branches of the quenching pipe 154 that has a diameter (i.e., inner diameter) approximately equal to the diameter of the transverse pressure pipes 150. Each of the branches 154 of the quenching pipe is attached and / or attached to a respective transverse pressure line 150 connecting clamp 158, which, as mentioned above, can be any suitable connecting block 158, especially or more specifically one that is mutually interconnected remove and disconnect the transverse pressure lines 150 and branches 154 of the quenching line for any desired reason, such as cleaning, or for any other purpose. The end parts of each of the branches 154 of the quenching pipe have a lateral guide support shown as position 184 (see FIG. 9) attached to the support means 134 (more specifically, the guard member shown here as 180). The side supports 184 can be made of any suitable material, preferably any thermally expanding material, which can be compatible with the metallurgical requirements for the support of the block 132 supplying the secondary quenching medium (or branches 154 of the quenching pipe), dependently relative to the supporting means 132 while providing some freedom of movement due to thermal expansion.

 Each of the branches 154 of the hardening pipeline has one or more holes or diaphragms 160, which are connected to the nozzle block shown at 164, to ensure the passage of quenching medium or substance from the branches 154 of the hardening pipe into the nozzle block 164 for subsequent injection and distribution over the catalyst layer 10. One or more holes or diaphragms 160 are designed to uniformly distribute the quenching medium (i.e., quenching liquid and / or quenching gas) over the catalyst layer.

 Each nozzle block 164 is connected to the openings of the quenching pipe 154 (and / or the quenching pressure pipe 142) so as to protrude from the bottom up towards the dome-shaped cover 14 of the reactor 11 and usually parallel to the longitudinal axis of the reactor 11. However, the intent and scope of the present invention include attachment at least one or more nozzle blocks 164 to the branches 154 of the hardening pipe (and / or pressure pipe 142 for hardening) so as to protrude from top to bottom or in the direction of the bottom of the reactor source, for example in the direction of the bottom of the reactor with a fixed catalyst bed. The direction of protrusion of one or more nozzle units 164 may depend on the desired direction of injection and / or distribution of the quenching medium or substance, such as in one direction or countercurrent with a stream of hydrocarbon feed passing through the catalyst bed.

 The support means 134 may be any suitable support means to support the quench media supply units 130 and 132 to a desired location within the catalyst layer 10 in the reactor 11, but preferably includes a containment element 180 and an element 188 connecting the support fixed to the enclosure 180. This enclosure the element 180 preferably has a configuration or construction that is similar to a cylindrical ring, with the element 188 connecting the support attached to its outer peripheral surface and to the inner indricheskoy side wall 12.

 As indicated previously, a pair of collector (or main) supports 182-182 are also connected to the enclosing member 180 (more specifically to the inner peripheral surface of the enclosing member 180) for connecting and / or interconnecting the primary hollow member 138 receiving the quenching medium or the pressure pipe 142 quenching to the enclosing member 180. As also indicated previously, the side supports 184 are connected to the enclosing member 180 (more specifically to the inner peripheral surface of the enclosing member 180) for connection and / or interconnecting the secondary quenching medium supply unit 132 (more specifically, the branches of the quenching pipe 154) with the guard member 180. The support member 188 justifies this preferred embodiment of the quenching system 39 inside and outside the reactor 11 (i.e., inside and outside cylindrical side wall 12 of the reactor 11) and is preferably made of any suitable material that can be compatible with metallurgical requirements and at the same time provides some freedom of movement due to thermal wow extension.

 The hydrotreating feed stream, including the liquid component and the hydrogen containing gas component, flows into the substantially densified hydrotreating catalyst bed at such a rate that the expansion of the substantially densified catalyst bed is limited to less than 10% in length beyond the substantially full axial length of the substantially densified hydrotreating catalyst bed in a stationary state . The volume of the hydrotreating catalyst is withdrawn from the reaction zone and the movement of a substantially densified hydrotreating catalyst layer in the reaction zone begins in a substantially piston mode. A replacement hydrotreating catalyst is added to the substantially compacted hydraulically treated catalyst bed moving downward in a substantially piston mode at such a rate as to significantly replace the volume of the hydrotreatment catalyst withdrawn. This procedure can be repeated at will repeatedly and even continuously or with continuous hydrotreatment.

 Another method is provided for hydrotreating a hydrocarbon feed stream that flows upward through a hydrogenation conversion reaction zone containing a substantially densified catalyst bed, which includes forming a plurality of annular mixing zones in a hydrogenation transformation reaction zone having a substantially densified catalyst bed, such that each annular mixing zone contains a hydrocarbon feed stream having a liquid component and a component of a hydrogen-containing gas and in which ltsevye mixing zones are concentric with respect to each other and coaxial with respect to the hydroconversion reaction zone. A hydrocarbon feed stream from each annular mixing zone is introduced into a substantially densified hydrotreating catalyst bed and an upward flow of hydrocarbon feed from each annular mixing zone through a substantially densified catalyst bed begins.

In addition, a method for increasing the activity of catalyst particles in the lower reaction zone of the catalyst bed during hydrotreating by contacting the catalyst bed in the hydrogenation reaction reaction zone with an upward stream of hydrocarbon feed having a liquid component and a component of a hydrogen-containing gas, which includes the steps of:
a) placing a plurality of catalyst particles in a hydrogenation reaction reaction zone to form a catalyst layer in which there is at least one upper reaction zone and at least one lower reaction zone;
b) the upward flow of hydrocarbon feeds having a liquid component and a hydrogen-containing gas component in the catalyst layer according to stage (a) until practically stationary conditions are reached, with the catalyst particles in the upper reaction zone having an increased level of activity, and the particles catalysts in the lower reaction zone have a lower level of activity compared to the upper level of activity;
c) removing the volume of the catalyst particles from the lower reaction zone of the hydrogenation conversion, wherein the withdrawn volume of the catalyst particles includes reduced density catalyst particles with an increased level of activity and increased density catalyst particles with a reduced level of activity;
d) separation of catalyst particles with high activity and lower density and catalyst particles with reduced activity and higher density;
e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a mixture of catalysts;
f) introducing a mixture of catalysts of stage (e) into the reaction zone of the hydrogenation conversion of stage (a); and
g) repeating steps (c) to (f) until the steady state conditions are achieved, with the catalyst particles in the lower reaction zone of the catalyst layer having an increased level of activity compared to the lower level of activity of step (b).

In addition, a method is provided for improving the hydrotreating catalyst’s ability to refine and / or demetallize in a substantially densified catalyst bed that moves down in the hydrogenation conversion reaction zone during hydrotreating (especially under equilibrium or stationary conditions) by contacting the hydrotreating catalyst in the hydrogenation conversion reaction zone with a hydrocarbon feed stream containing a liquid component and a hydrogen-containing gas component, which includes the stages:
a) removing the volume of catalyst particles from the hydrogenation conversion reaction zone, including a substantially densified hydrotreating catalyst layer, which actually moves downward by a piston stream inside the hydrogenation conversion reaction zone, wherein the withdrawn volume of catalyst particles includes reduced density catalyst particles with increased activity and increased density catalyst particles with decreased activity;
b) separation of catalyst particles with high activity and lower density from catalyst particles with reduced activity and higher density;
c) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a mixture of catalysts; and
d) introducing a mixture of catalysts of stage (c) into the hydrogenation conversion reaction zone of stage (a) to increase the hydrotreatment catalyst’s ability to refine and / or demetallize in a substantially densified catalyst bed which moves downward in the piston hydrogenation transformation reaction zone flow.

The objectives of the present invention are also achieved by the wide provision of a method of reducing the amount of hydrotreating catalyst that is necessary to improve the flow of hydrocarbon feed (or, in other words, to extend the life of the hydrotreating catalyst in the hydrogenation reaction zone) during hydrotreating by contacting the hydrotreating catalyst in the reaction hydrogenation transformation zone with an upward flow of hydrocarbon feed containing liquid component and component of hydrogen-containing gas. In accordance with the present invention, a decrease in the required amount of catalyst provides or allows the refinement of the hydrocarbon feed stream to the same extent as in the case of the amount of hydrotreatment catalyst that is needed to refine the hydrocarbon feed in a reactor with a single method for replacing the hydrotreatment catalyst. This method generally consists of stages:
a) removing the volume of catalyst particles from the hydrogenation conversion reaction zone, comprising a substantially densified hydrotreating catalyst layer, which initially has the form of a densified layer and which actually moves downward by a piston stream inside the hydrogenation conversion reaction zone, wherein the withdrawn volume of catalyst particles includes reduced density catalyst particles with increased activity and particles of a catalyst of increased density with reduced activity;
b) separation of catalyst particles with high activity and lower density and catalyst particles with reduced activity and higher density;
c) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a catalyst mixture having a volume that is less than the extracted volume of the catalyst particles; and
d) the subsequent introduction of the catalyst mixture into the hydrogenation conversion reaction zone so that the substantially densified catalyst bed, which moves downward in the piston flow hydrogenation transformation reaction zone, subsequently has a volume of compacted layer less than the original volume of the compacted layer.

In another aspect of the present invention, there is further provided a method for hydrotreating a stream of hydrocarbon feed moving upward through a hydrogenation conversion reaction zone containing a substantially densified catalyst bed, the method comprising the steps of:
a) the formation of a plurality of ring mixing zones in the hydrogenation reaction zone containing a substantially densified hydrotreating catalyst bed, such that each ring mixing zone contains a hydrocarbon feed stream comprising a liquid component and a hydrogen-containing gas component, and in which the ring mixing zones are concentric with respect to each other friend and coaxial with respect to the reaction zone of the hydrogenation transformation;
b) introducing a hydrocarbon feed stream from each annular mixing zone of step (a) into a substantially densified hydrotreating catalyst bed so that the hydrocarbon feed begins to rise up from each annular mixing zone through a substantially densified catalyst bed and to obtain a volume of catalyst particles in the reaction zone hydrogenation conversion, which includes low density catalyst particles with increased activity and high density catalyst particles with low activity Stu;
c) removing the volume of catalyst particles from the hydrogenation conversion reaction zone so that a substantially densified hydrotreating catalyst bed inside the reaction zone of the hydrogenation transformation begins to move downward with a piston stream;
d) separation of catalyst particles with high activity and lower density from catalyst particles with lower activity and higher density;
e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a mixture of catalysts; and
f) introducing a mixture of catalysts into the reaction zone of the hydrogenation conversion.

 The hydrogenation conversion system and / or the hydrogenation conversion reaction zone of a preferred embodiment of the present invention includes a catalyst which is described in detail below with the following subheading "Catalyst" and which can also operate in a fixed bed (i.e., the catalyst bed does not expand), in a moving bed fluidized bed, expanded bed, or fluidized bed.

Catalyst
In a preferred embodiment, the catalyst that is charged to reactor 11 preferably satisfies the following four basic criteria;
1) the catalyst has the corresponding catalytic activity and service life for a particular application (for example, demetallization, hydrodesulfurization, etc.);
2) the catalyst has such physical properties in which its random movements in the reactor 11 are minimized;
3) the catalyst has such physical properties in which its losses are minimized both at the stages of its transfer and in the reactor 11; and
4) the catalyst is sufficiently uniform in size, shape and density of particles to prevent their separation in size during normal operation.

 Preferably, the catalyst of the present invention has the corresponding catalytic activity and service life for a particular application (e.g., demetallization, hydrodesulfurization, etc.). For example, if the catalyst is to be used for demetallization, it must have sufficient activity during hydrodemetallization and a sufficient metal capacity (i.e., service life) in order to meet the purpose of demetallization without the use of uneconomical amounts of catalyst. The metal catalyst capacity preferably exceeds about 0.10 g of metal per cubic centimeter of bulk catalyst volume. The properties of the catalyst, which most strongly affect the catalytic activity and metal capacity, are as follows: porous structure (pore volume and pore size distribution); a base material (e.g., alumina or silica); catalytic metals (quantity, distribution and type - nickel, molybdenum, cobalt, etc.); surface area and particle size and shape.

 In addition, the catalyst of the present invention preferably has such physical properties that minimizes the accidental rise of its particles during the upward movement of the feedstock in the reactor 11. Since one of the advantages of the present invention is countercurrent contacting between the reactants and the catalyst, it is preferable to maintain the piston flow of the catalyst down along the entire length of the reactor 11. To minimize or prevent the expansion of the catalyst bed, eduyuschie properties of the catalyst: catalyst particle density (highest particle density possible is preferred, which complies with the catalytic activity of metals and container); particle size (the largest size is practically preferred); density of the base (increased density of the base is preferred to reduce skeletal buoyancy); and uniformity of size. One of the distinguishing features of the present invention is that the catalyst will not spread during inadvertent movement inside the reactor, but will still be fairly easy to move when transported by flow. Under the actual process conditions inside the reactor, substantially smaller catalyst particles may rise upward, while substantially larger particles may migrate downward. This interferes with the optimum piston flow of the catalyst. For this reason, the dimensional conditions for the catalyst of the present invention are narrower than the conditions for the catalysts of a fully densified or fixed bed and a fluidized bed.

 The catalyst of the present invention should additionally have such physical properties in which the loss of catalyst at the stages of its movement and in the reactor 11 is minimized. Destruction or abrasion of the catalyst or at the stages of movement or in the reactor 11 can have a significant detrimental effect on the characteristics of the reactor system itself and any subsequent equipment or technological installation. The following properties are critical for catalyst loss: catalyst abrasion (the minimum abrasion is an absolute requirement); fracture strength of the catalyst (maximum fracture strength of the catalyst is required; use of a very brittle catalyst is not allowed, which may be subject to excessive abrasion); the size and shape of the catalyst particles (spherical catalyst particles are preferred since they are more mobile and do not have sharp or sharp edges that break off); dust content (an absolute requirement is the minimum amount of dust in order to avoid the harmful effects of dust in the reactor 11 and in the subsequent equipment).

 The catalyst particles are sufficiently uniform in size, shape and density to prevent separation of the catalyst in size during normal operation. Typically, a narrow size range is required in order to prevent the size separation of the catalyst. The specific particle size of the catalyst is chosen so that it is close to the size at which the particles propagate in random directions, but not the size at which the particles propagate in random directions on their own or during boiling.

 All four of these basic criteria for selecting the catalysts of the present invention are important and are not mutually independent or mutually exclusive. These 4 main criteria must be balanced among themselves in order to optimize the catalyst for a particular application. For example, to minimize the spread of the catalyst in random directions, large particles of a very dense catalyst would be preferable. This contradicts properties that might be desirable when using a catalyst for demetallization of oil residues, where particles of small diameter with low density are needed. These contradictions must be balanced among themselves in order to ensure minimal catalyst distribution or boiling and at the same time to achieve the corresponding activity of the catalyst and its capacity in metals, minimal abrasion and minimal particle size separation.

 Due to the mutually exclusive requirements for the catalyst and due to the fact that each application is specific, the catalyst of the present invention can be any suitable catalyst that is able to assist in the implementation of the invention and to help achieve the objectives of the invention.

 The catalyst of the present invention provides an unobvious piston flow of a substantially densified catalyst bed (i.e., catalyst bed 10) during hydrotreating by contacting the substantially densified hydrotreating catalyst bed with a hydrocarbon feed stream (i.e., a liquid component and a hydrogen-containing gas component) that flows upwardly controlled to such an extent that it is sufficient to limit the expansion of a substantially densified hydrotreating catalyst layer by less than 10% Line over the axial length of the substantially packed catalyst bed hydrotreating stationary. More preferably, the expansion of the substantially densified hydrotreating catalyst bed is limited to less than 5%, most preferably less than 2%, or even less than 1% over substantially all of the axial length of the substantially densified hydrotreating catalyst bed in a stationary state. The flow rate of the hydrocarbon feed stream may be any suitable amount that is adjustable to such an extent that it is sufficient to limit the expansion of the substantially densified hydrotreating catalyst layer, preferably the flow rate ranges from about 0.01 ft / s (0.3 cm / s) to 10 ft / s (304.8 cm / s).

 The catalyst of the present invention more specifically provides an unobvious piston flow of a substantially densified hydrotreating catalyst bed when the volume of hydrotreating catalyst is discharged or transferred under conditions of a preferably laminar flow from the bottom of the substantially densified hydrotreating catalyst bed, although at the same time, the substantially densified hydrotreating catalyst bed maximally and optimally occupies at least at least about 50% of the volume, preferably from about 80 to 98% of the volume of the reactor 11 ( there is all internal available volume). The substantially densified hydrotreating catalyst bed of the present invention maximally and optimally occupies a volume inside the reactor 11 that is larger than the volume of the catalyst bed in the fluidized bed reactor, which has substantially the same total internal available volume as the reactor 11, and in which the volume of the catalyst bed in a fluidized bed reactor in the “failed” state of the bed, it occupies less than about 50% of the volume (maximum) of the total internal available volume of the fluidized bed reactor. Thus, the substantially densified hydrotreating catalyst bed maximally and optimally occupies at least about 50% of the volume, preferably from about 80 to 98 vol.% Of the internal available volume of the reactor 11. Most preferably, the substantially densified hydrotreating catalyst bed of the present invention maximally and optimally takes at least from about 85 to 98 vol% of the internal available volume of the reactor 11.

 In addition, the catalyst of the present invention specifically provides an unobvious piston flow of a substantially densified hydrotreating catalyst bed when the volume of the hydrotreating catalyst is withdrawn or transferred in a hydrocarbon feed stream under conditions of a preferably laminar flow from a central portion or section of a substantially densified hydrotreating catalyst bed from the lowermost bottom section of the bed and below the points of the plurality of annular mixing zones MZ containing a hydrocarbon feed stream (i.e., a liquid component nt and a component of hydrogen-containing gas). As indicated above, when the volume of the hydrotreating catalyst of the present invention is removed or transferred, so that the piston flow of the layer begins, it is removed or transferred preferably laminarly in the liquid hydrocarbon stream and removed from it near the impermeable zone (i.e., the non-perforated central plate 25) of the support 17 layer means and practically out of the flow path of LH-HG mixtures (i.e. LH-HG2, LH-HG3, etc.) arising from the mixing zones MZ (i.e. MZ2, NZ3, etc.). A particular volume (or amount) of catalyst that is discharged at any desired time from the bottom of a substantially densified hydrotreating catalyst layer may be any suitable volume (or amount) at which the objectives of the present invention are achieved. Preferably, as for example, by way of example only, the specific volume (or amount) of catalyst that is discharged at any desired time is the volume (or amount) varying from about 0.1% to 25% by weight of the substantially densified catalyst layer (i.e. there is a catalyst bed 10). The rate of removal of a particular volume (or amount) of catalyst may also be any suitable volume (or amount) at which the objectives of the present invention are achieved, such as the rate of removal at which the flow of catalyst (e.g., catalyst in a hydrocarbon feed stream) varies from 0.1 ft / s (3.05 cm / s) to 20 ft / s (610 cm / s), more preferably from about 0.1 ft / s (3.05 cm / s) to 10 ft / s ( 304.8 cm / s), and at a catalyst concentration varying from approximately 0.1 lb (45.4 g) catalysis torus / pound (454 g) of the catalyst suspension (i.e., the weight of the hydrotreating catalyst plus the weight of the hydrocarbon feed stream) to about 0.80 pounds (363 g) of the catalyst / pound (454 g) of the catalyst suspension, more preferably from about 0.15 (68 g) up to 0.60 pounds (272 g) of catalyst / pound (454 g) of catalyst suspension. As indicated above, the withdrawn catalyst can be conveniently replaced by introducing a volume of fresh catalyst through the top of the reactor 11 onto the catalyst bed 10. The rate of replacement or addition of the catalyst can be any rate of replacement or addition of the catalyst at which the objectives of the present invention are achieved, such as the flow rate of the replaced catalyst (i.e., the replaced catalyst in a stream of refined hydrocarbon feed, for example in gas oil), varying from about 0.1 ft / s (0.3 cm / s) to 20 ft / (610 cm / s), more preferably from about 0.1 ft / s (0.3 cm / s) to 10 ft / s (304.8 cm / s), and when the concentration of the replaced catalyst varies from approximately 0, 1 lb (45.4 g) of the replaced catalyst / lb (454 g) of the catalyst suspension (i.e. the weight of the hydrotreating catalyst plus the weight of the stream of refined hydrocarbon feed) to approximately 0.80 lb (363 g) of the replaced catalyst / pound (454 g) of the suspension catalyst, more preferably from about 0.15 (68 g) to 0.60 pounds (272 g) of catalyst / pound (454 g) of catalyst suspension.

 In a preferred embodiment of the present invention, the catalyst of the present invention includes an inorganic carrier, which may include zeolites, inorganic oxides such as silica, alumina, magnesium oxide, titanium dioxide and mixtures thereof or any amorphous refractory inorganic oxides from group II, III or IV elements or inorganic oxide compositions. More preferably, the inorganic support comprises a porous support material such as silica, alumina, silica-alumina or crystalline silica-alumina. One or more metals or metal compounds, such as oxides, are deposited onto this inorganic support or porous support material, these metals being selected from Groups Ib, Vb, VIb, VIIb and VIII of the Periodic System. Typical examples of these metals are iron, cobalt, nickel, tungsten, molybdenum, chromium, vanadium, copper, vanadium, copper, palladium and platinum, as well as combinations thereof. Molybdenum, tungsten, cobalt and nickel, as well as their combinations, are preferred. Suitable examples of the preferred catalyst type include nickel-tungsten, nickel-molybdenum, cobalt-molybdenum or cobalt-nickel-molybdenum deposited on a porous inorganic support selected from the group consisting of silica, alumina, magnesium oxide, titanium dioxide, zirconia, thorium dioxide, boron oxide or hafnium dioxide, or compositions of inorganic oxides such as aluminosilicate, silicon dioxide - magnesium oxide, aluminum oxide - magnesium oxide, and the like.

 The catalyst of the present invention may further include additives that alter the activity characteristics and / or capacity of the metals of the catalyst, such as (but not limited to) phosphorus and clays, including layered clays. Such additives may be present in any suitable amounts, depending on the particular application for the hydrogenation conversion process, including applied catalysts. Typically, such additives can be from about 0 to 10% by weight, based on the weight of the total catalyst (i.e., inorganic support plus metal oxide).

 Although metal components (e.g., cobalt, molybdenum, etc.) may be present in any suitable amount, the catalyst of the present invention preferably comprises from about 0.1% to 60% by weight of the metal components, based on the weight of the total catalyst (i.e. inorganic oxide carrier plus metal oxides) or more preferably from about 0.2% to 40% by weight of the total catalyst and most preferably from about 0.5% to 30% by weight of the total catalyst. Group VII metals are usually used in smaller amounts, in the range of about 0.1% to about 30 weight. %, more preferably from about 0.1% to 10 wt.%, and the metals of group VIB are usually used in large quantities, in the range from about 0.5% to 50 wt.%, more preferably from about 0.5% to 30 weight. %; although, as mentioned above, the total amount of metal components on a porous inorganic support is up to 60% by weight of the total catalyst (more preferably up to about 40% by weight). The atomic ratio of Group VIII and Group VIB metals can vary widely, preferably from about 0.01 to 15, more preferably from about 0.1 to 5. These atomic ratios will depend on the particular use of the hydrotreating catalyst and / or purification goals.

 The groups in the Periodic System referenced above refer to the Periodic Table of the Elements that is published in the Lange Chemistry Handbook (12th edition, edited by John D. Dean, copyright 1979 by McGraw Hill Inc.) or which is published in a brief chemical dictionary (10th edition), revised by Gessner G. Hawley (copyright 1981 by Lytton Publishing Publishing Inc.).

In a more preferred embodiment of the catalyst, the hydrotreating oxide catalyst or metal oxide component supported on an inorganic support or porous support material is molybdenum trioxide (MoO ₃ ) or a combination of molybdenum trioxide and nickel oxide (NiO), with molybdenum trioxide present in large quantities. The most preferred inorganic carrier is alumina. Molybdenum is present on the inorganic catalyst support (alumina) in amounts ranging from about 0.5% to 50% by weight, preferably from about 0.5% to 30% by weight, most preferably from about 1.0% to 20% by weight . % based on the total weight of the inorganic carrier and metal oxide (s). When nickel is present, its amount changes to approximately 30 weight. %, preferably from about 0.5% to 20% by weight, more preferably from about 0.5% to 10% by weight, based on the total weight of the inorganic carrier and the metal oxide (s). The hydrotreating oxide catalyst or metal oxide component can be prepared by any suitable technique, such as precipitation of metal oxide (s) from aqueous solutions onto porous inorganic support material, followed by drying and calcination. In general, catalyst preparation techniques are traditional and well known and may include impregnation, milling on runners, coprecipitation, and the like. followed by calcination.

The catalyst has a surface area (such as measured by the Brunauer-Emmett-Teller method) that is sufficient to achieve hydrotreatment goals for a particular application. The surface area is usually from about 50 square meters per gram (m ² / g) to 300 m ² / g, more typically from about 75 to 150 m ² / g.

 The average crush strength of the catalyst should be a minimum of approximately 5 pounds (2270 g). The crushing strength of the catalyst can be determined on a representative sample of catalyst particles. For example, a fixed number of particles (say 30 catalyst particles) are obtained from a static sample comprising a plurality of catalyst particles that will be tested during the hydrotreatment of the present invention. Each catalyst particle is sequentially positioned between two horizontal parallel steel plates. Then, a load is applied to the upper steel plate until the placed catalyst particle is crushed. The crush strength of a catalyst is the applied load at which a catalyst particle is crushed. This test is repeated for the remaining catalyst particles and the average crush strength of the catalyst is calculated. It is also preferred that no more than about 35 wt.% Of the catalyst particles have an average strength of less than about 5 pounds (2270 g); more preferably, not more than about 15 wt.% of the catalyst particles have an average strength of less than about 5 pounds (2270 g); and most preferably not more than about 0%.

 The catalyst of the present invention includes a plurality of catalyst particles that are uniform in size and preferably spherical with an average diameter varying from about 35 to 3 Tyler units (from 0.42 to 6.68 mm), more preferably from about 20 to 4 Tyler units ( from 0.83 to 4.70 mm) and most preferably from 14 to 5 Tyler units (from 1.17 to mm). The Tyler unit designations used here are taken from the table entitled "Tyler Standard Sieve Scales" of Reference 53, 1981 edition, published by CE Tyler Combustion Engineering, Inc., ul. Washington, South Norfolk. Connecticut.

 In the same way, preferably the catalyst particles have a uniformly smooth and rounded surface. Preferred forms include, for example, spheres, spheroids, egg particles, and the like. More preferably, the catalyst of the present invention is round particles comprising a plurality of catalyst particles having a size distribution such that at least about 90% by weight of these particles have a size ratio of less than about 2.0, more preferably 1.5 or less than 1.5 and most preferably equal to about 1.0. As used herein, the term "dimensional ratio" is a geometric term that is defined by the maximum length of a catalyst particle, relative to the width of the catalyst particle. "Maximum extent" is the maximum possible extent of a catalyst particle. This value is sometimes called the gauge size and it represents the maximum size in the maximum cross section of the catalyst particle. The “width” of the catalyst particle is the projection of the catalyst particle perpendicular to the maximum extent and represents the largest size of the catalyst particle in the direction perpendicular to the maximum extent.

The catalyst should have a particle size distribution such that the expansion of the catalyst layer 10 under conditions inside the reactor 11 is less than 10% of the length (more preferably less than 5% and most preferably less than 1% in length) over the almost total axial length of the substantially densified catalyst layer stationary hydrotreating. In order to obtain maximum reactor productivity, the catalyst particles have a narrow size distribution. The catalyst used in the hydrogenation process of the present invention generally includes a size range or size distribution such that at least about 90 wt.%, Preferably at least about 95 wt.%, More preferably at least about 97 wt.% the catalyst particles in the catalyst layer 10 have a diameter in the range from R1 to R2, while:
i) R1 has a value from about 1/64 inch (0.04 cm) (i.e. approximately corresponds to the size of the hole of the Tyler sieve 35 mesh) to 1/4 inch (0.63 cm) (i.e. approximately corresponds to the size of the hole of the Tyler sieve 3 mesh);
ii) R2 also has a value of approximately 1/64 inch (0.04 cm) (i.e. approximately corresponds to the size of the mesh hole of Tyler sieve 35 mesh) to 1/4 inch (0.63 cm), (i.e. approximately corresponds to the size of the mesh hole Tyler 3 mesh); and
iii) the ratio R2 / R1 has a value greater than or approximately equal to 1.0 and less than or approximately equal to 1.4 (or approximately equal to the square root of 2.0).

 More preferably, the catalyst particles in the catalyst layer 10 have a diameter in the range from R1 to R2, with each diameter of R1 and R2 having a value of from about 2/64 inches (0.08 cm), (i.e., approximately corresponds to a Tyler sieve opening size of 20 mesh ) up to 12/64 in. (0.48 cm), (i.e. roughly equivalent to the mesh size of Tyler sieve 4 mesh); most preferably from about 3/64 inch (0.12 cm) (that is, approximately corresponds to the size of the hole of the Tyler sieve 14 mesh) to 9/64 inches (0.36 cm) (that is, approximately corresponds to the size of the hole of the Tyler sieve 5 mesh); moreover, the ratio R2 / R1 has a value ranging from about 1.0 to 1.4 (or about the square root of 2.0).

 The catalyst used in the hydrogenation process of the present invention also broadly includes a particle size distribution such that a maximum of about 2.0 wt.% (More preferably a maximum of about 1.0 wt.% And most preferably a maximum of about 0.5 wt. % or less) of the catalyst particles have a diameter less than R1. The catalyst also has a particle size distribution such that a maximum of about 0.4 wt.% (More preferably a maximum of about 0.2 wt.% And most preferably a maximum of about 0.1 wt.% Or less) of the catalyst particles have a diameter less than R3, wherein R3 is less than R1 and the ratio R1 / R3 is about 1.4 (or about the square root of 2.0). The catalyst particles preferably have a maximum abradability of about 1.0 weight. % (more preferably a maximum of about 0.5 wt.% and most preferably a maximum of about 0.25 wt.% or less) from the catalyst particles to a diameter (i.e. passing through a Tyler sieve) having a value of R1, and additionally have a maximum abrasion is about 0.4 weight. % (more preferably a maximum abradability of about 0.2 wt.% and most preferably a maximum of about 0.1 wt.% or less) from the catalyst particles to a diameter (i.e. passing through a Tyler sieve) having the value R3, and here R3 (as mentioned above) is less than R1 and the ratio R1 / R3 is about 1.4 (or about the square root of 2.0). Note that the method for determining the abrasion is specified in the US standard AIS-T-EM Dee 4058-87. However, in the standard procedure, dust is removed up to a sieve of 850 μm (approximately 20 mesh). In the present methodology, this sieve has openings equal to the minimum particle size of the catalyst, which is desirable for a particular application, which is more specifically determined by the values of R1 and R3. Thus, by way of example only, for a catalyst with an agreed particle size range of about 10 to 12 mesh. Tyler can specify up to about 2.0 wt.% Dust (more preferably up to about 1 wt.% Dust) for a maximum size of 12 mesh. Tyler and up to 0.4 wt.% Dust (more preferably up to about 0.2 wt.% Dust) for a maximum size of 14 mesh. Tyler. Similarly, for a catalyst with a specified particle size range of about 6 to 8 mesh. Tyler can specify up to about 2.0 wt.% Dust (more preferably up to 1 wt.% Dust) for a maximum size of 8 mesh. Tyler and up to 0.4 wt.% Dust (more preferably up to about 0.2 wt.% Dust) for a maximum size of 10 mesh. Tyler. For a catalyst with a specified particle size range of about 10 to 12 mesh. Tyler can specify the abrasion up to about 1.0 wt.% (More preferably up to about 0.5 wt.%, Most preferably up to about 0.25 wt.%) For a maximum size of 12 mesh. Tyler and up to about 0.4 wt.% (More preferably up to about 0.2 wt.%, Most preferably up to about 0.1 wt.%) For a maximum size of 14 mesh. Tyler. Further, it is similar for a catalyst with a specified particle size range of from about 6 to 8 mesh. Tyler can specify the abrasion to about 1.0 wt.% (More preferably up to about 0.5 wt.%, Most preferably up to about 0.25 wt.%) For a maximum size of 8 mesh. Tyler and up to 0.4 wt.% (More preferably up to about 0.2 wt.% And most preferably up to about 0.1 wt.%) For a maximum size of 10 mesh. Tyler.

 The specific gravity of the catalyst particles is determined by the requirements of the hydrogenation conversion process. For the catalyst of the present invention, it is preferred that the particles have a uniform density. The term "uniform density" means that the density of at least 70 wt.%, Preferably at least 80 wt.% And more preferably at least 90 wt. % of individual catalyst particles did not change by more than about 10% of the average density of all catalyst particles; and more preferably, the density of the individual catalyst particles has not changed by more than about 5% of the average density of all catalyst particles. In a preferred embodiment, the catalyst of the present invention (i.e., fresh catalyst) has a particle density ranging from about 0.6 to 1.5 g / cc. cm, more preferably from about 0.7 to 1.2 g / cu. cm, most preferably from about 0.8 to 1.1 g / cu. see After the catalyst is at least partially spent, the particle density can vary from about 0.6 to 3.0 g / cu. cm, more preferably from about 0.7 to 3.0 g / cu. cm and most preferably from about 0.8 to 3.0 g / cu. see particle size determination will remain the same as above. Dust content and abrasion can increase during the hydrogenation transformation.

Although the catalyst of the present invention can be any catalyst defined above, the authors found that the most preferred catalyst for the optimal achievement of the objectives of the present invention has a combination of the following properties:
1. Porous inorganic oxide carrier.

 2. One or more catalytically active metals and / or additional catalytic additives deposited on a porous inorganic oxide carrier.

 3. The crushing strength is at least 5 pounds (2270 g).

 4. Homogeneous particle size, varying from about 6 to 8 mesh. Tyler.

 5. Dust content up to approximately 1 wt.% For a maximum size of 8 mesh. Tyler and up to 0.2 wt.% Dust for a maximum size of 10 mesh. Tyler.

 6. Abrasion up to about 0.5 wt.% For a maximum size of 8 mesh. Tyler and up to about 0.2 wt.% For a maximum size of 10 mesh. Tyler.

 7. Usually a uniform spherical shape.

 8. Homogeneous density, varying from about 0.7 to 3.0 cubic meters. cm.

 The authors unexpectedly found that a more preferred catalyst having or containing a combination of properties listed immediately above does not obviously provide the optimal nature of the piston flow of a substantially densified layer (i.e., catalyst layer 11) of a hydrotreating catalyst, which simultaneously expands by less than 10% in length (more preferably less than 1% in length) over the almost total axial length of the substantially densified hydrotreating catalyst bed in a stationary state, although (and at the same time Along with this, a substantially densified hydrotreating catalyst bed maximally and optimally occupies from about 50 vol.% to 98% of the volume of the reactor 11 (i.e., the entire internal available volume or volume of the reactor).

The specific type of porous base material or inorganic oxide support, the specific type of catalytically active metal, the porous structure, the surface area of the catalyst and the particle size of the catalyst - all these characteristics will depend on the intended specific application (e.g. demetallization, desulfurization, etc.) of the catalyst. Generally speaking, a more preferred catalyst comprises a porous inorganic oxide support selected from the group consisting of alumina, silica and mixtures thereof, and has a surface area in the range of about 75 to 150 m ² / g. A preferred catalyst includes a catalytically active metal (s) present in the form of oxide (s) deposited on a porous inorganic support. The oxide (s) of the catalytically active metal (s) or metal oxide component of the preferred catalyst is selected from the group consisting of molybdenum oxide, cobalt oxide, nickel oxide, tungsten oxide and mixtures thereof, and includes from about 0.5 to 50 wt.%, More preferably about 0.5 to 30% by weight of the total catalyst (i.e., inorganic support plus metal oxide (s)). In addition, a more preferred catalyst has an overall uniform size of spherical particles with an average diameter varying from about 20 to 4 mesh. Tyler. Although a spherical catalyst is preferred, an extrudate can also be used if it is very strong, say, has a crush strength of more than 5 pounds (2270 g). The absolute particle size of the catalyst may vary depending on the application, but the more preferred catalyst has a narrow distribution, as described above.

 From the discussion above, it will be clear to qualified practitioners that, although the catalyst particles of the present invention are of uniform size, shape and density, the chemical and metallurgical properties of the catalyst may vary depending on the hydrotreatment goals and the selected process conditions. For example, the catalyst selected for use in the demetallization process with maximum activity against hydrocracking will be completely different in nature than the catalyst selected for the task of maximum desulfurization and hydrocracking in the process. A type of catalyst, selected in accordance with this and having the above properties, is located in any reaction zone of the hydrogenation transformation. The hydrocarbon feed stream passes through the catalyst, preferably passes upstream through the catalyst in order to hydrotreat the hydrocarbon feed stream. More preferably, the catalyst is used with various embodiments of the present invention.

Example
A plurality of catalyst particles are charged into a reaction zone located inside the reactor, such as reactor 11. This plurality of catalyst particles forms a catalyst layer (such as catalyst layer 10 in FIGS. 1 and 2). This catalyst bed in the reactor rested on a truncated cone bed support, similar to the support shown generally at 17 in FIG. 1 and 2. An inlet distributor, such as a circular plate element 31 in FIG. 1 and 2 with a plurality of pipes 32 extending across the full cross section of the reactor below the truncated conical support of the layer, forms a pressure chamber or an inlet chamber between the inlet distributor and the truncated conical support of the layer. This truncated conical support of the catalyst bed includes a series of annular polygons that include a plurality of segmented plates (such as segmented plates 27 in FIGS. 4-6) connected to or formed with radial spoke elements, such as elements 26 in FIG. 3-6. Many segmented plates, each of which has a thickness of about 10 inches (25.4 cm) and a width of about 1.5 inches (3.8 cm), are attached to eight elements of the radial spokes. The mutually engaged segmented plates and radial spoke elements form a mesh structure in order to obtain substantially annular continuous mixing zones for receiving a hydrocarbon feed stream, and they overlap with a filter having openings of such an average diameter that is smaller than the size of the catalyst particles. Each mixing zone below the filter is usually uniform in thickness at the periphery.

Catalyst particles include a porous alumina support material or an inorganic support, alumina. An oxide component of a hydrotreating catalyst consisting of nickel oxide and / or molybdenum trioxide is applied to this porous alumina support material. The amount of molybdenum present on this porous alumina support material is 3% by weight based on the total weight of the porous alumina support material and the oxide component (s) of the hydrotreating catalyst. Nickel is contained in the porous alumina support material in an amount of about 1% by weight, based on the total weight of the porous alumina support material and the oxide component (s) of the hydrotreating catalyst. The surface area of these catalyst particles is about 120 m ² / g.

 The plurality of catalyst particles are generally spherical in shape and have an average diameter varying from 6 to 8 mesh. Tyler. The average crush strength of the catalyst particles is approximately 5 pounds (2270 g). The metal capacity of this plurality of catalyst particles is about 0.3 g of metals per 1 cubic centimeter of bulk volume of catalyst particles.

 This set of particles has a size distribution such that 98.5 weight. % of the particles in the catalyst bed have a particle size ratio of about 1.0 and a diameter in the range from R1 to R2, wherein: 1) R1 has a value of about 0.093 inches (0.24 cm) (i.e. approximately corresponds to a Tyler sieve hole size of 8 mesh) ; 2) R2 has a value of about 0.093 inches (0.24 cm) (that is, approximately corresponds to the size of the opening of Tyler sieve 6 mesh); and 3) the ratio R2 / R1 has a value equal to approximately the square root of 2.0, or about 1.414. The catalyst particles have a particle size distribution such that a maximum of about 1.0% by weight of the catalyst particles have a diameter less than R1. The catalyst also has a particle size distribution such that a maximum of about 0.2 wt.% Of the catalyst particles have a diameter less than R3, with R3 being less than 1 and the ratio R1 / R3 is about 1.414, or about a square root of 2.0.

 The catalyst particles preferably have a maximum abradability of about 0.5 wt.% From catalyst particles to a diameter (i.e. passing through a Tyler sieve) of value R1, and additionally have a maximum abradability of about 0.2 wt.% From catalyst particles to a diameter (i.e., passing through a Tyler sieve) having a value of R3, and here R3 is less than R1, and the ratio R1 / R3 is approximately 1.414 or approximately the square root of 2.0. Or in other words, for catalyst particles with a specified particle size range or distribution of about 6 to 8 Tyler mesh, the specified abrasion is up to about 0.5 wt.% For a maximum size of 8 Tyler mesh and up to 0.2 wt.% For a maximum size of 10 mesh Tyler.

 The catalyst particles have a maximum of up to about 1.0 wt.% For a maximum size of 8 Tyler mesh and up to 0.2 wt.% Dust for a maximum size of 10 Tyler mesh. In other words, for a catalyst with a specified particle size range or a size distribution of about 6 to 8 Tyler mesh, the indicated dust content in the catalyst particles will be up to about 1.0 wt.% For a maximum size of 8 Tyler mesh and about 0.2 weight. % for a maximum size of 10 Tyler mesh. The catalyst particles have a uniform density such that the average density of the catalyst particles is approximately 0.9 g / cu. cm.

The liquid component of the hydrocarbon feed stream is a heavy residue of atmospheric distillation, in which at least 95 vol.% Boil above 343 ^o C and in which a significant part (for example, 50% by volume) boils above 510 ^o C. This is a "heavy" hydrocarbon the feed has an unwanted metal content of about 90 ppm. by weight of heavy raw materials. The hydrogen-containing gas of the hydrocarbon feed stream is almost 97% pure hydrogen and is mixed with a heavy atmospheric residue in the ratio of 623 liters of hydrogen-containing gas under standard conditions per liter of heavy atmospheric residue, in order to obtain a hydrocarbon feed stream.

This hydrocarbon feed stream passes through an inlet distributor and is introduced into the reactor’s high pressure chamber at a flow rate varying from about 0.1 to 1.0 ft / s (3 to 30.48 cm / s). The pressure and temperature of the hydrotreating process were about 2,300 psi (161 at) and 400 ^° C., respectively. From this pressure chamber, the hydrocarbon feed stream enters the annular continuous mixing zone and is uniformly fed through the filter and into the catalyst bed so as not to cause local boiling or turbulent flows in the catalyst bed, especially close to the conical bed support that overlaps with the filter.

 The catalyst bed in the reactor contains a plurality of redistribution units (or quenching with hydrogen gas) located axially apart (see FIGS. 7-9 for an illustration of quenching blocks with hydrogen gas). When the hydrocarbon feed stream flows upward through the catalyst bed, hydrogen gas is emitted from the redistribution units that redistribute any hydrogen-containing gas that has become enclosed in a portion of the catalyst bed below (or in close proximity) the hydrogen redistribution units and further eliminates the possibility of localized heating spots turbulent flows or boiling in the upper part (especially above the blocks of redistribution of hydrogen) of the catalyst layer.

 The hydrocarbon feed stream leaves the reactor at a flow rate of about 3.6 ft / s (109.7 cm / s), and its quality is so improved that the metal content is about 3 ppm. by weight of the liquid hydrocarbon feed stream. When the hydrocarbon feed stream flows upward through the catalyst bed, the gamma radiation source in the catalyst bed in combination with the gamma radiation detector in the reactor indicates that the catalyst bed has expanded less than 10% of the length over the almost full axial length of the catalyst bed in a stationary state.

 After the reactor has been running for 1 week, approximately 7.25 cubic meters of catalyst particles (or approximately 3.3% of the weight of the catalyst bed) were discharged by laminar flow at a rate of approximately 3.6 ft / s (109.7 cm / s ) in a hydrocarbon feed stream through a J-shaped pipe (such as that shown at 29 in FIG. 1). The withdrawn catalyst in the hydrocarbon feed stream was contained in a concentration of about 0.5 lb / lb of catalyst suspension (227 g / 454 g) (i.e., the weight of the withdrawn catalyst plus the weight of the hydrocarbon feed stream). When this volume of catalyst particles was removed or moved from the bottom of the catalyst layer, this layer (i.e., a substantially densified catalyst layer) began to move in a piston mode.

 The withdrawn catalyst was replaced by introducing a comparable volume of fresh replacement catalyst through the top of the reactor. This fresh substitute catalyst is suspended in a purified hydrocarbon stream (e.g., gas oil) and introduced into the reactor at a catalyst substitution flow rate of about 3.6 ft / s (109.7 cm / s) and at a concentration of substitute catalyst / lb (454 d) catalyst slurries (i.e., discharged catalyst plus the weight of a stream of hydrocarbon feeds, for example gas oil, as a suspending medium).

 Although the present invention has been described herein with reference to specific embodiments thereof, many modifications, various changes and substitutions are implied, it being recognized that in some cases some features of the invention will be used without the corresponding use of other features, without deviating from the scope of the invention set forth herein.

Claims (21)

 1. The method of hydrotreating hydrocarbon feeds by passing a stream of hydrocarbon feedstock from bottom to top through a hydrogenation conversion reaction zone containing a substantially densified catalyst bed, characterized in that the catalyst located in the reaction zone includes a plurality of particles having an average diameter varying from about 35 to 3 Tyler mesh, and a size distribution such that at least about 90 wt.% Of the catalyst particles have a diameter in the range from R1 to R2, with R1 having a value in the range about 0.04 - 0.63 cm; R2 is about 0.04-0.63 cm; the ratio R2 / R1 varies from about 1.0 to 1.4; L / D size ratio less than about 2.0.  2. The method according to claim 1, characterized in that the catalyst particles have such a size distribution that a maximum of about 2.0 wt.% Of the catalyst particles have a diameter less than R1.  3. The method according to claim 1, characterized in that the catalyst particles have such a size distribution that a maximum of about 0.4 wt.% Of the catalyst particles have a diameter less than R3, with R3 being less than R1 and the ratio R1 / R3 is approximately 1.4.  4. The method according to claim 1, characterized in that the catalyst particles have a maximum abrasion of about 1% by weight of catalyst particles having a diameter in the range of R1.  5. The method according to claim 1, characterized in that it further comprises injecting the quenching agent into the catalyst.  6. The method according to claim 1, characterized in that to increase the level of activity of the catalyst particles in the lower reaction zone of the catalyst layer during hydrotreatment by contacting the catalyst layer in the reaction zone of the hydrogenation transformation with an upward flow of hydrocarbon feed having a liquid component and a component of a hydrogen-containing gas, additionally includes the steps of: a) placing a plurality of catalyst particles in a hydrogenation reaction reaction zone to form a catalyst layer in which at least th least one upper reaction zone and at least one lower reaction zone; b) the upward flow of hydrocarbon feeds having a liquid component and a hydrogen-containing gas component in the catalyst layer according to stage (a) until practically stationary conditions are reached, with the catalyst particles in the upper reaction zone having an increased level of activity and the particles catalysts in the lower reaction zone have a lower level of activity compared to the upper level of activity; c) removing the volume of the catalyst particles from the lower reaction zone of the hydrogenation conversion, wherein the withdrawn volume of the catalyst particles includes reduced density catalyst particles with an increased level of activity and increased density catalyst particles with a reduced level of activity; d) separation of catalyst particles with high activity and lower density from catalyst particles with lower activity and higher density; e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a mixture of catalysts; f) introducing the catalyst mixture of step (c) into the reaction zone of the hydrogenation conversion of step (a), g) repeating step (c) to (f) until stationary conditions are achieved, with the catalyst particles in the lower reaction the zone of the catalyst layer have an increased level of activity compared to the lower level of activity of stage (b).  7. The method according to claim 1, characterized in that to increase the ability of the hydrotreating catalyst to be upgraded and / or demetallized in a substantially densified catalyst bed that moves down in the hydrogenation transformation reaction zone during hydrotreatment (especially under equilibrium or stationary conditions ), by contacting the hydrotreating catalyst in the hydrogenation reaction zone with a hydrocarbon feed stream containing a liquid component and a hydrogen-containing component its gas, includes the steps of: c) withdrawing a volume of catalyst particles from a hydrogenation conversion reaction zone comprising a substantially densified hydrotreating catalyst layer that actually moves downward by a piston stream inside the hydrogenation conversion reaction zone, wherein the withdrawn volume of catalyst particles includes reduced density catalyst particles with increased activity and catalyst particles of increased density with reduced activity; d) separation of catalyst particles with high activity and lower density from catalyst particles with lower activity and higher density; e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a mixture of catalysts; and f) introducing a mixture of catalysts of step (e) into the hydrogenation conversion reaction zone of step (c) to increase the hydrotreatment catalyst’s ability to refine and / or demetallize in a substantially densified catalyst bed that moves downward in the hydrogenation transformation reaction zone of step (c) in piston flow.  8. The method according to claim 1, characterized in that to reduce the amount of hydrotreating catalyst, which is necessary to improve the flow of hydrocarbon feed or to extend the life of the hydrotreating catalyst, in the hydrogenation conversion reaction zone during hydrotreating by contacting the hydrotreating catalyst in the hydrogenation conversion reaction zone with a hydrocarbon feed stream containing a liquid component and a component of a hydrogen-containing gas, so that a reduction is necessary about the amount of catalyst provides or allows you to refine the flow of hydrocarbon raw materials to almost the same degree as in the case of the amount of hydrotreating catalyst, which is necessary to refine the flow of hydrocarbon raw materials in a reactor with a single method for replacing the hydrotreating catalyst, includes the stages: c) removing the volume of catalyst particles from a hydrogenation reaction reaction zone comprising a substantially densified hydrotreatment catalyst bed, which initially has the form of a densification layer and which actually moves downward by a piston stream inside the reaction zone of the hydrogenation transformation, wherein the withdrawn volume of catalyst particles includes reduced density catalyst particles with increased activity and increased density catalyst particles with reduced activity; d) separation of catalyst particles with high activity and lower density from catalyst particles with lower activity and higher density; e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a catalyst mixture having a volume that is less than the extracted volume of the catalyst particles; f) subsequently introducing the catalyst mixture into the hydrogenation conversion reaction zone so that the substantially densified catalyst bed, which moves downward in the hydrogenation conversion reaction zone in a piston flow mode, subsequently has a volume of compacted bed less than the original volume of the packed bed.  9. The method according to claim 5, characterized in that the injection comprises passing a quenching substance through a first passage zone having a first passage diameter, passing a quenching substance from the first passage zone to a second passage zone having a second passage diameter that is larger than the diameter of the first passage zone, the passage of the quenching substance from the second passage zone to the third passage zone having a third passage diameter that is less than the diameter of the second passage zone, and the passage of the quenching substance from the third passage discharge zone in a catalyst layer disposed in the hydroconversion reaction zone through which the hydrocarbon feed stream.  10. A method for hydrotreating a hydrocarbon feed stream passing from bottom to top through a hydrogenation conversion reaction zone comprising a substantially densified catalyst bed and a plurality of annular mixing zones in a hydrogenation transformation reaction zone containing a substantially densified hydrotreatment catalyst layer, each annular mixing zone containing a stream hydrocarbon feedstock, including a liquid component and a hydrogen-containing gas component, while the annular mixing zones are coherent with respect to each other and coaxial with respect to the hydrogenation reaction zone, comprising introducing a stream of hydrocarbon feed to raise the flow of hydrocarbon feed from each annular mixing zone through a substantially densified catalyst bed, characterized in that the catalyst is located in the reaction zone hydrogenation conversion, includes many catalytic particles having an average diameter varying from about 35 to 3 Tyler mesh and size distribution, in which at least about 90 wt.% of the catalyst particles have a diameter in the range from R1 to R2, wherein R1 has a value in the range of about 0.04 to 0.63 cm; R2 is about 0.04-0.63 cm; the R2 / R1 ratio varies from about 1.0 to 1.4 and the L / D size ratio is less than about 2.0.  11. The method according to claim 10, characterized in that the step of introducing a stream of hydrocarbon feed from each annular mixing zone into a substantially densified hydrotreating catalyst bed includes flowing a stream of hydrocarbon feed up from each annular mixing zone into a substantially densified catalyst bed hydrotreating at such a flow rate that the densified hydrotreating catalyst bed expands less than 10% in length over the almost full axial length of the substantially densified hydrotreating catalyst bed in the inpatient facility rated state.  12. The method according to claim 10, characterized in that it further includes withdrawing the volume of the hydrotreating catalyst from the reaction zone to allow the piston stream to move down the substantially densified hydrotreating catalyst layer inside the reaction zone and adding a volume of the replacement hydrotreating catalyst to this moving piston stream, a substantially densified hydrotreating catalyst bed to replace the volume of the hydrotreating catalyst.  13. The method according to claim 10, characterized in that it further comprises injecting the quenching agent into the catalyst.  14. The method according to p. 13, wherein the injection includes passing the quenching material through a first passage zone having a first passage diameter; passing the quenching material from the first passage zone to the second passage zone having a second passage diameter that is larger than the diameter of the first passage zone; passing the quenching material from the second passage zone to the third passage zone having a third passage diameter that is less than the diameter of the second passage zone; and passing the quenching substance from the third passage zone into the catalyst bed located in the reaction zone of the hydrogenation transformation, through which the flow of hydrocarbon feed passes.  15. The method according to claim 10, characterized in that to increase the level of activity of the catalyst particles in the lower reaction zone of the catalyst layer during hydrotreatment by contacting the catalyst layer in the reaction zone of the hydrogenation conversion with an upward flow of hydrocarbon feed having a liquid component and a component of hydrogen-containing gas, additionally includes the steps of: a) placing a plurality of catalyst particles in a hydrogenation reaction reaction zone to form a catalyst layer in which at least it least one upper reaction zone and at least one lower reaction zone; b) the upward flow of hydrocarbon feeds having a liquid component and a hydrogen-containing gas component in the catalyst layer according to stage (a) until practically stationary conditions are reached, with the catalyst particles in the upper reaction zone having an increased level of activity and the particles catalysts in the lower reaction zone have a lower level of activity compared to the upper level of activity; c) removing the volume of the catalyst particles from the lower reaction zone of the hydrogenation conversion, wherein the withdrawn volume of the catalyst particles includes reduced density catalyst particles with an increased level of activity and increased density catalyst particles with a reduced level of activity; d) separation of catalyst particles with high activity and lower density from catalyst particles with lower activity and higher density; e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a mixture of catalysts; f) introducing a mixture of catalysts of step (e) into the hydrogenation reaction reaction zone of step (a), g) repeating step (c) to (f) until stationary conditions are achieved, with the catalyst particles in the lower reaction the zone of the catalyst layer have an increased level of activity compared to the lower level of activity of stage (b).  16. The method according to p. 10, characterized in that to increase the ability of the hydrotreating catalyst to refine and / or demetallize in a substantially densified catalyst bed, which moves down in the hydrogenation transformation reaction zone during hydrotreating (especially under equilibrium or stationary conditions ), by contacting the hydrotreating catalyst in the hydrogenation conversion reaction zone with an upward stream of hydrocarbon feed containing a liquid component and a hydrogen-containing component gas, includes the steps of: c) withdrawing a volume of catalyst particles from a hydrogenation conversion reaction zone, comprising a substantially densified hydrotreating catalyst layer that actually moves downward by a piston stream within the hydrogenation conversion reaction zone, wherein the withdrawn volume of catalyst particles includes reduced density catalyst particles with increased activity and catalyst particles of increased density with reduced activity; d) separation of catalyst particles with high activity and lower density from catalyst particles with lower activity and higher density; e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a mixture of catalysts; f) introducing a mixture of catalysts of stage (e) into the hydrogenation transformation reaction zone of stage (c) to increase the hydrotreatment catalyst’s ability to refine and / or demetallize in a substantially densified catalyst bed which moves down in the piston hydrogenation transformation reaction zone flow.  17. The method according to p. 10, characterized in that to reduce the amount of hydrotreating catalyst, which is necessary to improve the flow of hydrocarbon feed or to extend the life of the hydrotreating catalyst, in the hydrogenation conversion reaction zone during hydrotreating by contacting the hydrotreating catalyst in the hydrogenation conversion reaction zone with an upstream hydrocarbon feed containing a liquid component and a component of a hydrogen-containing gas, so that a reduction is necessary the amount of catalyst provides or allows you to refine the flow of hydrocarbon raw materials to almost the same degree as in the case of the amount of hydrotreating catalyst, which is necessary to refine the flow of hydrocarbon raw materials in a reactor with a single method of replacing the hydrotreating catalyst, includes the steps of: c) removing the volume of catalyst particles from the reaction zone of the hydrogenation transformation, comprising a substantially densified hydrotreatment catalyst layer, which initially has the form tnennogo layer and which actually moves downward plug flow within the reaction hydroconversion reaction zone, wherein the withdrawn volume of particulate catalyst includes a reduced density of the catalyst particles with high activity and high density of catalyst particles having reduced activity; d) separating catalyst particles with high activity and density from catalyst particles with reduced activity and higher density; e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a catalyst mixture having a volume that is less than the extracted volume of the catalyst particles; f) the subsequent introduction of the catalyst mixture into the hydrogenation conversion reaction zone so that the substantially densified catalyst bed, which moves downward in the hydrogenation conversion reaction zone in the reciprocating flow mode, subsequently has a volume of the packed bed less than the original volume of the packed bed.  18. The method according to 14, characterized in that to increase the level of activity of the catalyst particles in the lower reaction zone of the catalyst layer during hydrotreating by contacting the catalyst layer in the reaction zone of the hydrogenation transformation with an upward flow of hydrocarbon feedstock having a liquid component of the supporting gas, further includes the stages : a) placing a plurality of catalyst particles in a hydrogenation reaction reaction zone to form a catalyst layer in which there is at least one ve a primary reaction zone and at least one lower reaction zone; b) the upward flow of hydrocarbon feeds having a liquid component and a hydrogen-containing gas component in the catalyst layer according to stage (a) until practically stationary conditions are reached, with the catalyst particles in the upper reaction zone having an increased level of activity and the particles catalysts in the lower reaction zone have a lower level of activity compared to the upper level of activity; c) removing the volume of the catalyst particles from the lower reaction zone of the hydrogenation conversion, wherein the withdrawn volume of the catalyst particles includes reduced density catalyst particles with an increased level of activity and increased density catalyst particles with a reduced level of activity; d) separation of catalyst particles with high activity and lower density from catalyst particles with lower activity and higher density; e) mixing the catalyst particles with high activity and lower density with fresh catalyst particles to obtain a catalyst mixture; f) introducing the mixture of catalysts of step (e) into the hydrogenation reaction reaction zone of step (a), and g) repeating steps (c) to (f) until stationary conditions are achieved, with the catalyst particles in the lower the reaction zone of the catalyst layer have an increased level of activity compared to the lower level of activity of stage (b).  19. A catalyst for hydrotreating a hydrocarbon feed by contacting a substantially densified catalyst bed with an upstream hydrocarbon feed comprising a liquid component and a hydrogen-containing gas component, characterized in that the catalyst comprises a plurality of catalyst particles having an average diameter ranging from about 35 to 3 Tyler's mesh; and a size distribution in which at least about 90 wt.% of the catalyst particles have a diameter in the range from R1 to R2, with R1 having a value in the range of about 0.04 to 0.63 cm, R2 has a value of about 0.04 - 0.63 cm, the ratio R2 / R1 varies from about 1.0 to 1.4 and the size ratio L / D is less than about 2.0, while the catalyst particles have such a size distribution that a maximum of 2.0 weight .% of the catalyst particles have a diameter less than R1, and a maximum of about 0.4 wt.% of the catalyst particles have a diameter less than R3, and R3 is less than R 1 and the ratio R1 / R3 is approximately 1.4, and when the catalyst particles are located in the hydrocarbon conversion zone, a substantially densified hydrotreating catalyst layer is formed and, when the hydrocarbon feed stream passes from the bottom up through the substantially densified catalyst layer, the piston flow begins of this catalyst bed when the volume of the catalytic particles is discharged from the bottom of the hydrocarbon conversion zone.  20. The catalyst according to claim 19, characterized in that the catalyst particles have a maximum abrasion of about 0.4% by weight of catalyst particles having a diameter in the range of R3, wherein R3 is less than R1 and the ratio R1 / R3 is about 1.4.  21. A method for hydrotreating a hydrocarbon feed stream passing from bottom to top through a hydrogenation conversion reaction zone comprising a substantially densified catalyst bed, a plurality of annular mixing zones in a hydrogenation transformation reaction zone comprising a substantially densified hydrotreatment catalyst layer, each annular zone the mixture contains a hydrocarbon feed stream comprising a liquid component and a hydrogen-containing gas component, wherein the annular mixing zones are concent coherent with respect to each other and coaxial with respect to the hydrogenation reaction zone, comprising introducing a hydrocarbon feed stream from each annular mixing zone into a substantially densified hydrotreating catalyst bed to allow upward flow of the hydrocarbon feed from each annular mixing zone through a substantially densified catalyst bed characterized in that it comprises the following steps: injecting a quenching agent into a substantially densified hydrotreating catalyst bed; withdrawing the volume of catalyst particles from the hydrogenation conversion reaction zone to allow the substantially densified hydrotreating catalyst bed to move downwardly with the piston stream within the hydrogenation transformation reaction zone, and adding the volume of catalyst to the hydrogenation transformation reaction zone to replace the withdrawn volume of catalyst particles. Priority on points:
04/29/94 - according to claims 1 - 4, 10 - 12, 19 and 20;
07/11/94 - according to claims 5, 9, 13, 14, 21;
11.21.94 - according to claims 6 - 8, 15 - 18.

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