• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    An asphaltene-containing oil hydrodesulfurization process employing an upstream catalyst and a downstream catalyst in series. The downstream catalyst comprises supported Group VI and Group VIII metals together with a promoting amount of Group IV-B metal in the form of particles whose surface is shaped by multiple elongated alternating grooves and protrusions. The upstream catalyst comprises Group VI and Group VIII metals without promotion with Group IV-B metal in the form of particles which may or may not be similarly shaped. Beds of the downstream and upstream catalyst may be diposed in the same or in different reactors. The adaptation of the grooved particle configuration to the promoted catalyst composition provided the early development of a plateau-like aging curve which was not achieved by the adaptation of the grooved shape to a non-promoted catalyst.
    公开号:SU843765A3
    申请号:SU782629452
    申请日:1978-06-27
    公开日:1981-06-30
    发明作者:А.Фрайер Джеймс；К.Лиз Генри；Д.Маккинни Джоел；Дж. Мецджер Кирк；А.Параскос Джон
    申请人:Галф Рисерч Энд Дивелопмент Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR HYDROELECTRONIZATION OF ASPHALTENI METAL CONTAINING OIL.  my invention / in fig.  4 is another embodiment of the invention.  The non-promoted top or first of the catalyst layers consists of metals of the VI and VIII groups deposited on an uncracked carrier.  Combinations of metals such as cobalt molybdenum, nickel tungsten, and nickel molybdenum are used, the preferred combination being cobalt molybdenum nickel.  The catalyst contains 5-30 weight. % of metals of groups VI and VIII, preferably 8-20 wt. % and composition includes highly porous non-destructive carrier material.  Alumina is the preferred carrier material, but other carriers can be used, for example silica, alumina and silica-magnesium oxide.  Using the upstream catalyst feedstock, a significant amount of sulfur and metals is recovered from the original oil.  The bottom layer of the catalyst contains metals of the VI and VIII groups and the promoter is titanium in the amount of 110 weight. %, preferably 2.58, 0 weight. %, which can be obtained by. impregnation of the carrier with metal salts.  For impregnation, you can use a solution of titanium tetrachloride in an amount of more than 8-10 weight. % in n-heptane. .  The use of more titanium may be detrimental to hydrodesulfurization activity.  The shaped catalyst particles are solid and have a surface with at least one cavity and an Omni protrusion.  In a preferred embodiment, these particles are elongated extrudates with a plurality of alternating elongated straight or curved surface depressions or gyri and protrusions.  The number of troughs is 1-8, preferably 3-4.  The depressions form a series of elongated protrusions, which can be rounded, extending along the length of the catalyst particle, so that on the transverse section -.  The axis of the particle is visible. many surface protrusions connected by intersection with the formation of a single structural catalyst that ensures the strength of the particle in the region of intersection.   The diameter of the catalyst particle can be expressed as twice the smallest size from the central axis to the surface.  The measurement is performed from the depth of the slit, which is now the deepest surface depression between the protrusions, to the central axis of the particles. The diameter size for the shaped catalyst particles is usually 0.042-017 cm, preferably 0.046-0.127 cm, and most preferably 0.051-0.102 cm.  The corresponding radial dimensions should be half of these values and be 0.021-0.085 cm, preferably 0.023-0.064 cm, and most preferably O, 025-0.051 cm.  It has been established that if a hydrodesulfurization catalyst with four protrusions formed by four cavities and having a certain diameter size equal to 0.07 cm, is destroyed in violation of the shape of the initial particles, thereby forming smaller, granular particles, 0.0419-0.0841 cm in size then the activity of the catalyst does not increase in spite of an increase in such a ratio of surface area to volume.  On the other hand, it is known that grinding a catalyst of a similar composition in the form of cylindrical particles with a usual diameter of 0.08 cm to particles of the same size increases its activity.  It is generally believed that any reduction in particle size increases the activity of the catalyst due to the concomitant increase in the ratio of surface area to volume.  Therefore, the absence of an increase in activity with a decrease in the size of the shaped particles indicates that the shaped particles in the size range of the proposed method already possess optimal activity due to the shape of the particles.  Since grinding does not increase the activity of the catalyst, the use of particles of a smaller size is unprofitable, since this will only lead to an increase in the pressure drop in the system without an accompanying improvement in activity.  Possible reasons for the optimal activity associated with the size of a portion of the profiled catalyst used in the process are that the shape of the particle can increase the surface tension and the contact time associated with this, increase the wettability of the particle with the liquid in the reactor using downward or jet flow, in relation to the residence time of the liquid or with a wetting ability for non-particulate particles.  The profiled catalyst provides multiple points of contact between adjacent particles, thereby reducing the surface of the inoperative nozzle, increasing the free volume of the reactor and increasing the wetted zones of the particles.  Used profiled. catalyst provides unexpected advantages when working with high mass fluid velocities.  In the experiment on hydrodesulfurization of residual oil, the shaped particles of the catalysts with four grooves and a diameter of 0.07 cm show an advantage at 12 ° C compared to cylindrical particles having a normal diameter of 0.09 cm at the hourly volume velocity of the liquid 0.88, while the liquid flow rate, equal to 4, the temperature advantage increases to 13, while maintaining the rest of the process conditions unchanged.  Under operating conditions, the mass rate can be increased at any given space velocity by increasing the thickness of the catalyst bed.  At a fixed volumetric rate and a fixed volume of catalyst, an increase in the thickness of the catalyst bed is equivalent to a decrease in the layer diameter.  Therefore, enhancing the benefits of increasing mass velocity makes the use of shaped catalyst particles particularly advantageous in a reactor whose diameter is smaller than the diameter of the reactor containing non-shaped particles.  Since the mass velocity is defined as the weight of the fluid flow per unit cross sectional area of the reactor per unit of time, the mass velocity increases exponentially with a decrease in the diameter of the reactor at a given space velocity.  In addition, the shaped catalyst particles of this method can be defined as concave particles, as opposed to. convex particles.  A solid geometric body is considered to be convex if all pairs of points lying inside or on the surface of a solid body can be connected by a straight line, which is completely located within the surface.  The spherical and cylindrical particles are convex.  - Conversely, a solid geometric body is considered concave if at least one pair of points lying inside or on the surface of the solid can be connected by a straight line that is not completely inside or on the surface of the solid.  The geometric volume of the smallest convex solid containing a concave solid must be greater than the geometric volume of the concave solid.  Assuming that Vy is equal to the volume of a minimal convex solid that a particular concave solid may contain, and V is equal to the volume of the contents of a concave solid, the resulting concavity coefficient C can be expressed like this: Vx The concave geometrical solid has a concavity coefficient greater than one.  The average concavity of the shaped catalyst particles is 1.01-1.35, preferably about 1.03 or 1.05-1.25, most preferably 1.10-1.20.  Attitude external. the surface to the volume of the shaped particles of the catcher is usually 31.1 and 78.1 cm, preferably 39.4 and 70.8 cm.  The inner surface of the profiled catalyst may be 100-350 MVr; The shaped particles of the catalyst can have about (the pore volume of pores is 0.3-0.85, with more than half of this volume having pores with a radius of between 50 and 300 A). The shaped particles of the catalyst provide a higher free volume of the reactor than cylindrical particles.  If VP is the volume of each particle, including the pore volume multiplied by the number of particles, and Vy is the volume of the total free space of the reactor, including the pore volume, then the fraction of the free volume is V, + VP.  In a reactor containing shaped catalyst particles, the proportion of free volume is 0.200, 95, preferably 0.25-0.55.  In the process of hydrodesulfurization, a partial pressure of hydrogen of 70-350 kg / cm, preferably 70-210 kg / cm - or 105175 kg / cm is used.  The gas circulation rate is 17.3-356 cT. MVlQO l, preferably 35.6-178 Art. m / lOO l.  In a preferred embodiment, the circulating gas contains -85. % or more of hydrogen.  The molar ratio of hydrogen to feedstock is 4: 1 and 80: 1.  The temperature in the reactor is 316 ° C and 482 ° C, preferably 343 ° C and 427 ° C.  To compensate for the loss of catalyst activity as it ages, the temperature in the reactor is increased.  The temperature should be low enough so that no more than 30% usually, in preferably no more than 10.15 or 20 weight. % of the original oil with a temperature of 35 ° C for 43 ° C, was cracked to a product boiling at a temperature below 343 ° C.  .  The volumetric flow rate of the liquid in each reactor is 0.1-10 or 0.2-1.25 oil volumes per hour per catalyst volume.  The term asphaltene and metal-containing oil in the proposed method is understood as crude oil, or stripped oil after atmospheric or vacuum distillation, containing essentially all residual crude oil asphaltenes.  Other asphalt-containing oils, such as coal liquids and oils extracted from oil shale and tar sands, may be used. Asphaltenes have a relatively low ratio of hydrogen to carbon compared to low-boiling oils and usually contain most of the metallic components present in all raw materials, for example , nickel and vanadium.  Since most catalyst is about. The desulfurization is highly active in demetallization, as well as in desulfurization, the first of the layers, the immobilized catalyst, removes a significant amount of nickel and vanadium from the raw materials along with a significant amount of sulfur.  These metals tend to deposit on the catalyst and reduce its desulfurizing activity.  The removal of nickel and vanadium is the cause of the mandatory deactivation of the first catalyst, while the deposition of coke will only slightly reduce its activity. Since stripped of atmospheric or vacuum distillation of oil contains essentially all the asphaltene fraction of crude oil from which they originate. t, they usually contain from 95 to 99 weight. % or more nickel and.  Vanadium: Crude Oil.  The content of nickel, vanadium and sulfur in petroleum residual oils may vary widely.  For example, nickel and vanadium can be 0.002-0.03 weight. % (20-300 ppm or more of petroleum, while sulfur may be from about 2 to about 7 wt. % or more.  In the first or non-promoted catalyst, the nickel gradually accumulates on the catalyst particle and in nadium, leading to blocking of the catalyst pores.  After blockage of the pores, the rate of catalyst aging ceases to be gradual and increases dramatically until the end of the catalyst cycle.  According to the method, a layer of non-promoted catalyst is placed over the layer of a promoted catalyst.  These layers may be placed in a single reactor or in separate ones. reactors.  When placed in separate reactors, the advantage is achieved by including a first unpromoted catalyst between the first stage and the second promoted catalyst stage and the gas evaporation stage.  Most metals and sulfur are recovered from crude oil in the first stage. The first cause of deactivation of the second stage catalyst is coking due to more severe hydrodesulfurization conditions.  In two-step hydrodesulphurisation processes, residual oil fractions using non-promoted catalysts and with an intermediate stage to remove contaminating side ta3OBs, such as hydrogen sulfide, ammonia, gaseous hydrocarbons, and with gradually increasing temperatures in each stage to compensate for catalyst aging, it is usually observed that catalyst aging rate and coke formation on the catalyst are significantly higher in the second stage than in the first.  It.  high coking formation at the second stage can be explained to molecules. ryy basis.  In the first stage, the peripheral alkyl groups present in the initial asphaltene and the resin co-molecule: create spatial difficulties that tend to prevent the polycondensed annular intramolecular layer of the residue molecules from contacting with the catalyst. However, sulfur in asphaltene molecules found in aromatic wood is not removed in the first stage and must be removed in the second stage.  Due to the absence of alkyl groups of molecules in the raw material of the second stage, the contact of carbon atoms of the aromatic nucleus and catalyst is closer than in the first stage.  When this happens desulfurization, accompanied by enhanced coke formation.  In method 2, it has been shown that in the second stage of the degassing of the promoter, the promoted catalyst shows improved desulfurization activity along with inhibition of coke formation and, accordingly, a decrease in the aging of the catalyst.  .  In addition, the use in the second stage of catalyst promotion is carried out to a lower consumption of hydrogen in comparison with the use of a non-promoted catalyst in the second stage.  This economy of hydrogen is consistent with data showing that the promoted catalyst in the second stage is significantly more selective with respect to the reaction and desulfurization process than the non-promoted catalyst.  Thus, the promoted catalyst causes significantly fewer side reactions,.  for example, hydrogenolysis, aromatic saturation, etc. d.  Since the cycle of operation of promoted and non-promoted catalysts in the first desulfurization operation is limited by the deposition of metals and since the advantage of desulfurization for the promoted catalyst in the first stage is relatively small and decreases in proportion. catalyst aging, the promoted catalyst is not used as the top catalyst. .  A less expensive non-promoted catalyst is used as the upper catalyst.  Since the life cycle of the lower catalyst is limited by coking, and since the particular advantage of a promoted catalyst is its high resistance to coke, the promoted catalyst is used. after the non-promoted catalyst bed.  In addition, the promoted catalyst is subject to rapid autoregeneration at the second stage by local removal of surface coke after increasing the hydrogen pressure.  ; The promoted catalyst accelerates the addition of hydrogen to the surface coke with increasing hydrogen pressure, the solution thereby part of the surface coke and partially regarating the catalyst.  It has been found that the promoter catalyst exhibits an improved kinetic effect on the catalytic reduction of coke after increasing the pressure of hydrogen compared to the non-promoted catalyst.  Experiments have shown that the time spent on increasing the activity of the non-promoted second stage katashizator by increasing the pressure of hydrogen is much more than is required for the promoted catalyst.  Therefore, a promoted catalyst can provide an advantage when working at the second stage not only due to the initial inhibition of the formation of coke, but also due to the elimination of coke from the catalyst by hydrogenation with the dissolution of coke and transferring it to the processed oil.  To reactivate to the second stage of the second stage, the parallel pressure of hydrogen must be increased to at least 3.5 kg / cm.  preferably up to 10.5 kg / cm, and the second stage should operate at this elevated pressure at least. measure within 24 hours  Since the total pressure in any reactor with a promoted catalyst is determined by the design features of the reactors, the hydrogen pressure in the industrial plant cannot be arbitrarily increased to reduce the amount of coke on the catalyst.  However, in an industrial plant, it is possible to de-catalyze the catalyst by intermittently increasing the purity of hydrogen in a reactor with a promoted catalyst to increase the portion of hydrogen pressure without increasing the total pressure in the regtor, i.e. this process can be carried out for the catalyst regeneration using a source of hydrogen with a higher partial pressure at a constant total pressure.  In the experiments used promoted catalyst containing, regardless of the form of alumina, impregnated with molybdenum, nickel and titanium, and the alumina base is impregnated with 3 weight. % nickel, 8 wt. % molybdenum and.  5 wt. % titanium.  Non-promoted catalyst used in the experiments, regardless of the form contains 0.5 weight. % nickel, 1 wt. % cobalt, 8 wt. % molybdenum, the rest is alumina. I All cylindrical catalysts, regardless of composition, have a diameter of 0.08.  cm, and the shaped catalysts, regardless of the composition, have four longitudinal protrusions and depressions on the surface of the particle with a concavity factor equal to 1.15; twice the smallest distance from the surface to the central axis is 0.07 cm.  Example.  The raw material used is the residual fraction of Kuwaiti oil boiling above.  This fraction containing 3.8 wt. % sulfur, subjected to hydrodesulfurization at a hydrogen pressure of 136.5 kg / cm and hydrogen consumption 133.2 Art.  l  One part of the raw material is passed in the form of a jet with hydrogen down through the first-stage reactor containing cylindrical non-promoted catalyst particles.  Another part of the raw material is passed in the form of a jet stream with hydrogen through the reactor of the first stage of the same size, containing the shaped particles of non-promoted catalyst.  At the beginning of the experiment, the volumetric flow rate of the fluid in each reactor is 0.88 fluid volumes per hour per catalyst volume.  The temperature in each reactor is gradually increased as the catalyst ages, adjusting it so that a constant stream of liquid product containing 0.95 wt. % sulfur. .  Circulation of the reagent through each reactor is continued for about 12 days at the indicated volume. speed, after which the volumetric rate is increased to 4, while increasing the mass velocity.  At higher space velocities, the temperature in each reactor in a similar way gradually increases as the catalyst ages, so that a constant stream of liquid product containing 2.4 wt. % sulfur.  In all experiments (FIG.  1) the temperature required for the process in the reactor, containing em-shaped catalyst particles.  below the required temperature in the reactor containing cylindrical particles of the catalyst.  This indicates a relatively higher catalytic activity of the profiled catalyst particles.  In addition, that perraturnoe; The advantage of a profiled catalyst is greater at a higher volumetric rate.  Thus, prior to the increase in the space velocity, the temperature advantage in favor of the shaped catalyst is 1. while the average temperature advantage in favor of the shaped catalyst at the first three points after the change in the space velocity is 13 ,.  Thus, the established temperature advantage for a shaped catalyst, which increases substantially with increasing mass velocity, shows that the desired effect can be achieved by using shaped catalyst particles in a reactor of relatively small size, since a large decrease in reactor diameter causes an exponential increase in mass velocity. at a given volumetric rate.  Example 2 The starting point is a stream leaving the first stage of hydrodesulphurisation,.  where the hydrodesulfurization is subjected to the raw materials of example 1.  The sulfur content in this stream is 1.09 wt. %  In these experiments, individual parts of the first-stage product, together with 73 tbsp.  L of hydrogen is passed down as a jet stream over separate layers of cylindrical and shaped promoted catalysts for a period longer than 50 days with a volumetric fluid hourly rate of 1 and under a pressure of 147 kg / cm to achieve a degree of both serrations of about 71%.  At the end of this period. the profiled catalyst is 8.3C more active than the cylindrical catalyst when receiving both sulfuric products containing 0.37 wt. % sulfur.  After that, the volumetric fluid hourly rate increased to 3.99, having carried out a fourfold increase in the mass velocity.  The temperatures in each reactor are then adjusted to obtain a product containing 0.65 wt. % sulfur.  Under these conditions, the shaped catalyst is 12.2 ° C more active than the cylindrical catalyst, since the expected difference in activity is.  this suggests that, at the second stage, the activity of the profiled promoted catalyst improves with increasing mass.  speed compared to the same, but not promoted catalyst, Example 3.  Use the raw materials of example 2.  The promoter catalyst has cylindrical particles.  The test was carried out in separate reactors of the same diameter by passing the source oil in the form of a jet bottom {single stream through the catalyst.   In each experiment, the volumetric fluid consumption per hour is 1.0 volume of oil per hour per volume of catalyst, hydrogen pressure 147 kg / ptf and hydrogen consumption 72 degree.   l  In each experiment, the temperature is gradually increased as the catalyst ages to produce a liquid product containing 32 wt. % sulfur.  In the whole period of the experiment (FIG.  2) the temperature in the reactor containing the shaped catalyst was lower than the temperature in the reactor containing the cylindrical catalyst, which indicates a relatively higher catalytic activity of the shaped catalyst.  In addition, the relative temperature advantage in favor of the shaped catalyst increases with increasing catalyst life.  For example, relative temperature. The advantage for a shaped catalyst is 5, with a catalyst lifetime of 5 days and slightly increases to b, with a catalyst lifetime of 20 days.  With a lifetime of 30 days, the temperature advantage slightly increases to 7, however after 40 days the temperature advantage increases to 10 ,.  After 53 days, the temperature advantage in favor of the shaped catalyst reaches 11.7 seconds and the temperature curve becomes substantially flat.  The temperature curve for the shaped catalyst begins to level off between 9 and 20 days and has a relatively flat configuration after 20 days, while the temperature curve for the cylindrical catalyst does not reach a flat configuration during this period.  Since the aging of the second stage catalyst is almost entirely due to the formation of coke, the equalization of the temperature curve for the shaped catalyst indicates that the coke on the shaped catalyst reached an equilibrium level, t. e.  old coke is removed from the catalyst at the same rate at which the new is deposited on it.  At this stage of catalyst life, such a situation for a cylindrical catalyst is not reached.  The use of a reactor of relatively small diameter to increase the mass velocity of the liquid over the promoted catalysts provides not only the mass velocity advantage for the shaped catalyst, but also allows the reactor to maintain a higher pressure and, consequently, a higher hydrogen pressure, which also contributes to reducing coke formation.  . .  In contrast to expansion. temperature advantages for the shaped promoter catalyst j used in the second stage, relative to the cylindrical promoter catalyst (see  FIG.  1 and 2), there is no comparable expansion of the temperature advantage in the first. steps of hydrodesulfurization.  residual oil using shaped and cylindrical non-coated catalysts, as well as no comparable flat aging curve configuration for a shaped non-promoted catalyst.  In this connection, an advantage for a filmed catalyst is characteristic of a second-stage operation using a catalyst promoted with titanium.  Thus, with.  comparing FIG.  and 2 it should be noted that the promoted second stage shaped catalyst allows for a lower operating temperature than the first stage catalyst.  Example 4  Experiments were conducted to illustrate the high activity of the shaped catalyst particles described.  When conducting these experiments, a sample of fresh particles of a shaped non-promoted catalyst is ground for. destroying particle shapes and producing conventional spherical particles between 0.0419 and 0.0841 cm.  Grinding increases. surface to volume ratio QT 53 cm to 94 cm.  Hydrodesulfurization activity is investigated. shaped particles.  For comparison, a fresh sample of non-promoted cylindrical extrudates. Combs that have a surface to volume ratio of 53 cm are crushed to form conventional, spherical particles between 0.0419-0.0841 cm, with a surface to volume ratio of 94 cm. The activity to hydrodesulfurization of the crushed cylindrical extrudates is examined for comparison with the activity for uncut cylindrical extrudates.  All hydrodesulfurization tests were carried out using the feedstock. in example 1, with the supply of 0.88 volumes of liquid per hour to the volume of the crystallizer.  The sulfur content is reduced to 0.95 weight. %  The table shows the temperatures required to maintain this level of sulfur in the product for various periods of service of the catalyst.
    Data tables show that, when using unmixed cylindrical particles, a temperature of about 13–16.5 ° C is required, than the temperature required for using unground, shaped particles. This temperature advantage is also illustrated in FIG.
    Although. Necessary temperature for cylindrical particles
    decreases during crushing; it follows from the table that crushing of shaped particles does not affect the required temperature, despite the increase in grinding of the surface-to-volume ratio.
    FIG. Figure 3 shows a variant of the invention in which the individual layers of the non-promoted and promoted catalyst are used sequentially in a single reactor. The feed oil is charged via line 1, fresh, and / or recirculating hydrogen is fed via line 2 to the top of the reactor 3. The reactor 3 contains a moving catalyst bed consisting of two layers, including the top layer 4 of untreated catalyst, which can be as shaped particles. Although it is shown in the figure that most of the catalyst is in the reactor in the upper layer 4, the amount of catalyst in the upper layer may be equal to or less than the catalyst in the lower layer 5, which contains the shaped particles of the promoted catalyst. Sweet oil and gases are removed along line b. Another variant of the proposed invention (Fig. 4) —the layers of an unprompted and promoted catalyst are sequentially located in separate reactors. The original oil is fed through line 7, recycling hydrogen through line 8 to the top of the reactor of the first stage 9, containing a fixed bed of non-promoted catalyst, particles of which can be, in particular, shaped. The flow from the first stage through line 10 is directed to the evaporation chamber 11, from which line 12 removes hydrogen contaminated with hydrogen sulfide and ammonia. Fluid through line 13 is sent to the second stage reactor 14. Fresh and / or recirculating hydrogen in reactor 14 is fed through line 15. The second stage reactor 14 contains a stationary layer 16
    C / Yun Cflymfu, cymtw
    权利要求:
    Claims (2)
    [1]
    FIG. f promoted catalyst in the form of | shaped particles. The product of the second stage is discharged through line 17. The invention The method of hydrodesulfurizing asphaltene- and metal-containing oil at 315-482® C and a hydrogen pressure of 7035p atm by passing the feedstock and hydrogen downstream through the upper and lower layers of the catalyst arranged in series and containing metals of the VI and VIII groups on a non-cracking carrier and in the lower layer in the form of a promoter of 1-10 wt.% of titanium, characterized in that, in order to increase the efficiency of the process by lowering the hydrodesulfurization temperature in the lower layer, in the latter, a catalyst is used in the form of elongated particles having one or several cavities and one or several protrusions in the cross section, characterized by a concavity factor of 1.01-1.35 and the shortest distance between the depth of the cavity and the central axis of the catalyst particle in the cross section equal to 0.0210, 0845 cm. Sources of information taken into account during the examination 1.Orochko DM and others. Hydrogenation processes in oil refining “M. Chemie, 1971, p. 225-230.
    [2]
    2. US patent 3876530, class, 208 - 210, published. 1975.3. Patent SHE 3968027, cl. 208-210, pub. 1976 (prototype).
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    类似技术:
    公开号 | 公开日 | 专利标题
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    同族专利:
    公开号 | 公开日
    CA1114319A|1981-12-15|
    US4116817A|1978-09-26|
    JPS5411906A|1979-01-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3674680A|1970-03-09|1972-07-04|Standard Oil Co|Process and catalyst for hydroprocessing a resid hydrocarbon|
    US4028227A|1974-09-24|1977-06-07|American Cyanamid Company|Hydrotreating of petroleum residuum using shaped catalyst particles of small diameter pores|
    US3990964A|1973-08-03|1976-11-09|American Cyanamid Company|Hydrotreating of petroleum distillates using shaped catalyst particles|
    US3985643A|1973-08-30|1976-10-12|Mobil Oil Corporation|Demetalation and desulfurization of oil in separate catalytic zones|
    US3968027A|1975-04-28|1976-07-06|Gulf Research & Development Company|Multi-stage hydrodesulfurization utilizing a second stage catalyst promoted with a group IV-B metal|US4421633A|1981-03-13|1983-12-20|Mobil Oil Corporation|Low pressure cyclic hydrocracking process using multi-catalyst bed reactor for heavy liquids|
    JPH0116127Y2|1982-04-01|1989-05-12|
    US4619759A|1985-04-24|1986-10-28|Phillips Petroleum Company|Two-stage hydrotreating of a mixture of resid and light cycle oil|
    US4657663A|1985-04-24|1987-04-14|Phillips Petroleum Company|Hydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage|
    US4734186A|1986-03-24|1988-03-29|Phillips Petroleum Company|Hydrofining process|
    US4707246A|1986-11-14|1987-11-17|Phillips Petroleum Company|Hydrotreating catalyst and process|
    US4762814A|1986-11-14|1988-08-09|Phillips Petroleum Company|Hydrotreating catalyst and process for its preparation|
    MY139580A|2002-06-07|2009-10-30|Shell Int Research|Shaped catalyst particles for hydrocarbon synthesis|
    AU2003298268B2|2002-11-04|2007-11-29|Shell Internationale Research Maatschappij B.V.|Elongated shaped particles; use as a catalyst or support thereof|
    EP2106293B1|2007-01-18|2016-03-30|Shell Internationale Research Maatschappij B.V.|Catalyst, catalyst precursor, catalyst carrier, preparation and use of thereof in fischer-tropsch synthesis|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/810,857|US4116817A|1977-06-28|1977-06-28|Hydrodesulfurization process employing a promoted catalyst|
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