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    • 专利摘要:
    PROCESS FOR THE HYDROPROCESSING OF A HYDROCARBON FEED. The present invention relates to a process for the hydroprocessing of hydrocarbons in a combined target pretreatment and a selective ring opening unit, in which the target pretreatment comprises at least two stages in a single circuit for recycling the liquid. The process operates as a total liquid process in which all of the hydrogen dissolves in the liquid phase. Heavy hydrocarbons and light cycle oils can be converted in the process to provide a liquid product that has an amount greater than 50% in the diesel boiling range, with properties that satisfy the use of low sulfur diesel.
    公开号:BR112013018931B1
    申请号:R112013018931-2
    申请日:2012-02-13
    公开日:2021-03-02
    发明作者:Hasan Dindi；Alan Howard Pulley；Luis Eduardo Murillo
    申请人:Refining Technology Solutions, Llc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to a process for the hydroprocessing of hydrocarbon feeds in total liquid reactors with a single liquid recycling circuit. BACKGROUND OF THE INVENTION
    [002] The worldwide demand for diesel, in particular for ultra-low sulfur diesel (ULSD), has increased rapidly with the growth of transport fuels and a decrease in the use of fuel oil. Transport fuel rules have been established to substantially reduce sulfur levels in diesel fuels. There are other pending call rules to also reduce the sulfur content in off-road diesel. Therefore, there is an increasing need for hydrocarbon feeds to be used as a raw material for diesel production, including ULSD.
    [003] A refinery produces a number of hydrocarbon products that have different uses and different values. It is desired to reduce production or improve products of lower value for products of higher value. Two examples of lower value products are cycle oils and heavy hydrocarbons.
    [004] Cycle oils have historically been used as a mixing stock in fuel oil. However, these oils cannot be directly mixed with today's diesel fuels due to their high sulfur content, high nitrogen content, high aromatics (particularly high polyaromatics), high density, and low cetane value.
    [005] Heavy hydrocarbon feeds contain compounds with high boiling points and, in general, are characterized as having high asphaltene content, high viscosity and high density. Currently, producers of heavy hydrocarbon mixtures have few options for their use, and the options available have relatively low commercial value.
    [006] Cycle oils and heavy hydrocarbons are used in heating oils. However, the sulfur content of these hydrocarbons may limit their use due to calls from recent regulations for stricter standards for heating oil sulfur.
    [007] Hydroprocessing, such as hydrodesulfurization and hydrodenitrogenation, are used to remove sulfur and nitrogen, respectively, from hydrocarbon feeds. An alternative operation of hydroprocessing is hydrocracking, which was used to fractionate heavy hydrocarbons (high density) in lighter products (lower density) with the addition of hydrogen. If the nitrogen content is too high in the mixture of hydrocarbons entering the hydrocracking process, the zeolitic hydrocracking catalyst can be poisoned. In addition, if hydrocracking is too severe, significant amounts of naphtha and lighter hydrocarbons, which are considered to be lower value products, can be produced.
    [008] Conventional three-phase hydroprocessing units used for hydrocracking and high pressure hydrotreating, commonly known as leaky bed reactors, require hydrogen from a vapor phase to be transferred to the liquid phase that is available to react with a hydrocarbon feed on the catalyst surface. These units are expensive, require large amounts of hydrogen, many of which must be recycled through expensive hydrogen compressors, and result in significant coke formation on the catalyst surface, and catalyst deactivation.
    [009] Alternative hydroprocessing approaches include hydrotreating and hydrocracking in an open flow scheme as proposed by Thakkar et al., In “LCO Upgrading A Novel Approach for Greater Value and Improved Returns“ AM, 05-53, NPRA, (2005). Thakkar et al., Describes an improvement of a light cycle oil (LCO) in a mixture of diesel and gasoline products from liquefied petroleum gas (LPG). Thakkar et al., Describes the production of a low sulfur diesel (ULSD) product. However, Thakkar et al. Uses traditional leaky bed reactors, which require large amounts of hydrogen and large process equipment, such as a large gas compressor for circulating hydrogen gas. Significant amounts of light gas and naphtha are produced in the described hydrocracking process. The diesel product represents only about 50%, or less, of the total liquid product using the LCO feed.
    [010] Kokayeff, in US patent 7,794,585, describes a process for hydrocracking and hydrotreating the hydrocarbon raw materials in a "substantially liquid phase", which is defined as the feed flow that has a liquid phase greater than one phase gaseous. More specifically, hydrogen can be present in a gas phase up to a maximum of 1,000% saturation. Kokayeff teaches that these high quantities are necessary for hydrogen to be consumed, hydrogen is available from the gas phase. As a result, the Kokayeff reaction system is the leaky bed. The separation of gases occurs after hydrocracking and before recycling part of the liquid product. As a result, hydrogen gas is lost from the reactor effluent, which can be significant, since Kokayeff teaches the addition of hydrogen well above the hydrogen saturation limit of the liquid.
    [011] It is desirable to present a process for the hydroprocessing of hydrocarbon feeds in a smaller and simpler system, without the addition of a gas phase or gas separation, which can result in the loss of hydrogen in the process. It is also desirable to present a process for the hydroprocessing of hydrocarbon feeds for the production of low sulfur diesel with a good yield and to achieve the multiple desirable diesel properties, such as low density and low polyaromatics and high number of cetane. It is also desired to present a process to improve the lower-value refinery hydrocarbons for higher-value products. BRIEF DESCRIPTION OF THE INVENTION
    [012] The present invention relates to a process for the hydroprocessing of a hydrocarbon feed, which comprises: (a) contacting the feed with (i) a diluent and (ii) hydrogen for the production of a feed mixture / diluent / hydrogen, in which hydrogen is dissolved in the mixture to provide a liquid feed, (b) contact of the feed / diluent / hydrogen mixture with a first catalyst in a first treatment zone, referred to herein as a “ pre-treatment target ”, for the production of a first product effluent, (c) the contact of the first product effluent with a second catalyst, in a second treatment zone, referred to herein as a“ selective ring opening zone ”, For the production of a second product effluent, and (d) recycling a portion of the second product effluent as a stream of the recycling product for use in the diluent in step (a) (i) at a rate of recycling to from about 1 to about 8, where the first treatment zone comprises at least two stages, the first and second treatment zones are the zones of the total liquid reaction, and the total amount of hydrogen fed to the process is more than 100 normal liters of hydrogen per liter of feed.
    [013] The process of the present invention operates as a total liquid process. By "total liquid process", it is understood at present that all the hydrogen present in the process can be dissolved in the liquid. By “zone of the total liquid reaction”, it is understood at present that no hydrogen of the gas phase is present in the contact zone (catalyst bed) of the feed / diluent / hydrogen mixture with the first catalyst and the second effluent of the product of the second catalyst.
    [014] The catalysts in the target pretreatment and each of the zones of the selective ring opening comprise a metal and an oxide support. The metal is a non-noble metal selected from the group consisting of nickel and cobalt, and their combinations are preferably combined with molybdenum and / or tungsten. The first catalyst support is a mono- or mixed metal oxide, preferably selected from the group consisting of alumina, silica, titania, zirconia, diatomite, silica-alumina and combinations of two or more of these. The second catalyst support is a zeolite, amorphous silica, or a combination of these.
    [015] In the first treatment zone, a hydrocarbon feed is subjected to the target pretreatment to reduce its nitrogen, sulfur and aromatics. The reduction of the nitrogen content of the feed in the target pre-treatment zone is critical in order to avoid poisoning the second catalyst in the second treatment zone. In the second treatment zone, the effluent from the first treatment zone is subjected to a selective or reinforced opening of the ring to improve its cetane value and to reduce its density (volume expansion). BRIEF DESCRIPTION OF THE FIGURES
    [016] Figure 1 is a flow diagram illustrating an embodiment of the target pretreatment / selective ring opening process of the present invention. DETAILED DESCRIPTION OF THE INVENTION
    [017] The present invention relates to a process for the hydroprocessing of a hydrocarbon feed, comprising: (a) contacting the feed with (i) a diluent and (ii) hydrogen for the production of a feed mixture / diluent / hydrogen, in which hydrogen is dissolved in the mixture to provide a liquid feed, (b) contact of the feed / diluent / hydrogen mixture with a first catalyst in a first treatment zone, referred to herein as a “ pre-treatment target ”, for the production of a first product effluent, (c) the contact of the first product effluent with a second catalyst, in a second treatment zone, referred to herein as a“ selective ring opening zone ”, For the production of a second product effluent, and (d) recycling a portion of the second product effluent as a stream of the recycling product for use in the diluent in step (a) (i) at a rate of recycling to from about 1 to about 8, where the first treatment zone comprises at least two stages, the first and second treatment zones are the zones of the total liquid reaction, and the total amount of hydrogen fed to the process is more than 100 normal liters of hydrogen per liter of feed.
    [018] Suitable hydrocarbon feeds for use in the present invention include a hydrocarbon feed, which has a density of at least 0.910 g / ml at a temperature of 15.6 ° C, and a boiling point at range of about 375 ° C to about 650 ° C. A suitable feed has an API gravity in the range of about 24 to about 0. The feed can have high levels of one or more contaminants, such as sulfur, nitrogen and metals. For example, the feed may have a sulfur content in the range of 1,500 to 25,000 parts per million by weight (wppm), and / or a nitrogen content greater than 500 ppm.
    [019] In one embodiment, the hydrocarbon feed is a "heavy hydrocarbon feed" which, as used herein, means a feed comprising one or more hydrocarbons, which has an asphaltene content of at least 3%, with based on the total weight of the feed, a Conradson carbon content in the range from about 0.25% to about 8.0% by weight, a viscosity of at least 5 cP, and a boiling point at range from about 410 ° C to about 650 ° C. The asphaltenes content of heavy hydrocarbons, in general, varies from about 3% to about 15%, and can be as high as 25%, based on the total weight of the feed.
    [020] In one embodiment of the present invention, light cycle oil is used as the feed for the production of low sulfur diesel. Light cycle oil has a cetane number in the range from about 15 to about 26. Light cycle oil also has a polyaromatic content in the range from about 40% to about 50%, in weight, and monoaromatics content in the range from about 20% to about 40% by weight, and the total aromatics content, in the range from about 60% to about 90% by weight. The light cycle oil has a density of at least 0.930 g / mL at a temperature of 15.6 ° C.
    [021] Surprisingly, the process of the present invention can reduce the density of the product to about 0.860 g / ml or less, at a temperature of 15.6 ° C, and achieve the desirable diesel properties, including the lower sulfur content at 50 wppm, preferably less than 10 wppm, and the cetane number increased by at least 12 points in relation to the hydrocarbon feed.
    [022] Preferably, the cetane number is at least 27 and can be from 27 to 42, and can still be higher. Other desirable properties of the diesel product include a minimum freezing point of -10 ° C and a minimum flash point of 62 ° C. The diesel product is produced by distilling the total liquid product (after the gases are removed) and through the removal of the naphtha product (fraction of the total liquid product, which has a maximum boiling point of 200 ° C).
    [023] Heavy hydrocarbons and light cycle oils are some examples of suitable hydrocarbon feeds for use in the process of the present invention. These feeds are available, such as from refineries, to improve through the pretreatment process targeting total liquid / selective opening of the ring of the present invention. These and other hydrocarbon feeds useful in the present invention are known to those skilled in the art.
    [024] The diluent comprises, consists essentially of, or consists of a stream of the recycling product. The flow of the recycling product is a part of the product mixture - according to the product's effluent - which is recycled and combined with the hydrocarbon feed, before or after the feed comes into contact with hydrogen, preferably before the feed comes into contact. contact with hydrogen. The recycling product stream provides at least part of the diluent at a recycling rate in the range from about 1 to about 8, preferably at a recycling rate from about 1 to about of 5.
    [025] In addition to the flow of the recycling product, the diluent can comprise any other organic liquid that is compatible with the feeding of heavy hydrocarbons. When the diluent comprises an organic liquid in addition to the flow of the recycle product, preferably the organic liquid is a liquid in which the hydrogen has a relatively high solubility. The diluent may comprise an organic liquid selected from the group consisting of light hydrocarbons, light distillates, naphtha, diesel and combinations of two or more of these. More particularly, the organic liquid is selected from the group consisting of propane, butane, pentane, hexane, or combinations thereof. When the diluent comprises an organic liquid, the organic liquid is normally present in an amount not exceeding 90%, based on the total weight of the feed and the diluent, preferably 20 to 85% and, most preferably, 50 to 80%. Most preferably, the diluent consists of a stream of the recycling product, which includes the dissolved hydrocarbons.
    [026] In the first stage of the process of the present invention, a feed comes in contact with a diluent and hydrogen. The feed can come in contact with hydrogen first, then with the diluent or, preferably, first with the diluent and then with the hydrogen for the production of a feed / diluent / hydrogen mixture. The feed / diluent / hydrogen mixture is placed in contact with a first catalyst, first a first treatment zone for the production of a first product effluent.
    [027] The first treatment zone is a pre-treatment target. By "target pretreatment" is presently a hydrotreatment process, in which a specific target in the content of sulfur, nitrogen, aromatics and / or metal in the product is found through the selection of the catalyst and / or the control of a or more of the following reaction conditions (for example, temperature, pressure, spatial velocity, and the like) More particularly, the target pretreatment provides a first product effluent which, after the second treatment zone and the separation steps, the diesel product has the specifications for a sulfur content of less than 50 wppm, a nitrogen content of less than 10 wppm, aromatics: a polyaromatic content of less than 10% by weight and a total aromatic content of less than 40% by weight, heavy metal content less than 1 wppm. The separation steps include the removal of the gases from the second product effluent and the distillation to remove the naphtha product.
    [028] The target pretreatment process may include one or more of the following procedures based on hydrocarbon feed: hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodeoxygenation and hydrogenation, depending on the feed, at various stages of the reaction with a single circuit of liquid recycling. By "single recycling circuit" it is understood at present a part (based on the selected recycling rate) of the second product effluent that is recirculated from the outlet of the second treatment zone to the entrance of the first treatment zone. Therefore, all catalyst beds in the process are included in the single recycling loop. There is no separate recycling for just the first treatment zone or just the second treatment zone.
    [029] The first treatment zone comprises at least two stages. “At least two stages” means, at present, two or more (multiple) catalyst beds in series. The catalyst is loaded for each bed. A single phase can be a reactor that contains a catalyst bed. The first treatment zone can comprise at least two reactors, each reactor contains a catalyst bed, in which the reactors are in liquid communication, for example, through an effluent line. The first treatment zone can comprise at least two catalyst beds in a reactor, for example, a column reactor. Other variations, including those that have more than two stages, can be easily appreciated and understood by a person skilled in the art. In a column reactor or other single vessel that contains two or more catalyst beds or between several reactors, the beds are physically separated by a catalyst-free zone. Preferably, hydrogen can be fed between the beds to increase the hydrogen content in the product effluent between stages. The hydrogen dissolves in the liquid effluent from the catalyst-free zone so that the catalyst bed is a zone of the total liquid reaction. Therefore, fresh hydrogen can be added to the liquid mixture of the feed / diluent / hydrogen or effluent from a previous reactor (in series) in the catalyst-free zone, where the fresh hydrogen dissolves in the mixture or effluent before contact with the catalyst bed. A catalyst-free zone before a catalyst bed is illustrated, for example, in US patent 7,569,136.
    [030] The second treatment zone comprises one or more stages, where the term "stages" is defined in the previous paragraph. The second treatment zone provides manipulation of the “selective” or “reinforced” ring of aromatic compounds. Through selective or reinforced manipulation of the ring, it is understood an increase in the ring opening activity in relation to the hydrogenation of the polyaromatics to the monoaromatics or to the saturated ring compounds or partially or completely opening the saturated rings in linear or branched hydrocarbons . The selectivity and degree of such manipulation of the ring is a surprising improvement over the process described by Thakkar et al., In the article NPRA, see above, page 8, line 9.
    [031] A column reactor can include the first treatment zone and the second treatment zone. This reactor contains at least two stages (catalyst beds) for the first treatment zone and one or more stages for the second treatment zone. Between each stage, there is a catalyst-free zone that can be used, for example, to add and dissolve the fresh hydrogen in the liquid effluent.
    [032] Target pretreatment and enhanced ring handling of aromatic compounds with increased ring opening activity contributes to high hydrogen demand and consumption. In the first and second treatment zones, the total amount of hydrogen fed to the process is greater than 100 normal liters of hydrogen per liter of feed (N L / L) or greater than 560 scf / bbl. Preferably, the total amount of hydrogen fed to the process is 200 to 530 N L / L (from 1,125 to 3,000 scf / bbl), most preferably from 250 to 360 N L / L (1,400 to 2,000 scf / bbl). The combination of the feed and the diluent is capable of supplying all the hydrogen in the liquid phase, without the need for a gaseous phase for such high hydrogen consumption. That is, the treatment zones are the zones of the total net reaction.
    [033] The process of the present invention can operate in a wide variety of conditions, from medium to extreme. The temperature for the first treatment zone and the second treatment zone varies from about 300 ° C to about 450 ° C, preferably from about 300 ° C to about 400 ° C and, most preferably, from about 350 ° C to 400 ° C. The pressure for the first treatment zone and the second treatment zone varies from about 3.45 MPa (34.5 bar) at 17.3 MPa (173 bar), preferably from about 6.9 to 13.9 MPa (from 69 to 138 bar).
    [034] A wide range of suitable concentrations of the catalyst can be used in the first and second treatment zones. Preferably, the catalyst is from about 10 to about 50% by weight of the contents of the reactor for each zone of the reaction. The hydrocarbon feed is fed to the first treatment zone at a rate to provide an hourly spatial liquid velocity (LHSV) from 0.1 to about 10 hr-1, preferably from about 0.4 to about 10 hr-1, more preferably from about 0.4 to about 4.0 hr-1.
    [035] The liquid product produced by the process of the present invention can be separated into a naphtha product and a diesel product, where the diesel product meets the criteria for mixing medium distillate fuels with a low sulfur content, such as such as low-sulfur diesel. The liquid product comprises less than 50% by weight of the total product boiling in the naphtha range (naphtha product) and correspondingly at least 50% of the product boiling in the diesel range (diesel product), preferably less than 25% by weight of the total product is a naphtha product and at least 75% of the product is a diesel product.
    [036] In conventional processes, the ring opening is separated from the pretreatment as two separate processes, due to the poisoning effect of the sulfur and nitrogen compounds on the ring opening catalysts. Therefore, such processes require a separation step to remove hydrogen sulfide and ammonia, especially ammonia, from a hydrotreated product. In an alternative process, the gas is separated from the product effluent before the product effluent is recycled. These two separations are undesirable, as they can cause the loss of hydrogen from the effluent of the products. In the present invention, hydrogen is recycled with the flow of the recycled product, without the loss of hydrogen in the gas phase.
    [037] In the pretreatment zone of the present invention, organic nitrogen and organic sulfur are converted into ammonia (hydrodenitrogenation) and hydrogen sulfide (hydrodesulfurization), respectively. There is no separation of ammonia and hydrogen sulphide from the remaining hydrogen from the effluent from the pre-treatment zone (first product effluent), before the effluent is fed into the second zone (ring opening). The resulting ammonia and hydrogen sulfide after the pre-treatment step are dissolved in the first effluent of the liquid product. In addition, the flow of the recycled product is combined with fresh feed, without the separation of ammonia and hydrogen sulfide and remaining hydrogen from the second effluent of the products. In addition, the first and second catalysts do not exhibit deactivation or coke on the catalyst surface.
    [038] The process of the present invention also operates as a total liquid process. By "total liquid process", it is understood at present that all the hydrogen present in the process can be dissolved in the liquid. A “total liquid reactor” is a reactor in which all the hydrogen is dissolved in the liquid phase when the liquid phase is in contact with the catalyst bed. There is no gaseous phase. The reactors in the first and second treatment zones are the total liquid reactors.
    [039] The reactors in the first and second treatment zones are two-phase systems in which the first and the second catalyst are in the solid phase, and the reactants (feed, diluent, hydrogen) and the effluents of the products are all in the liquid phase. Each reactor is a fixed bed reactor and can be a piston flow, tubular or other design, which is packaged with a solid catalyst (ie, a packaged bed reactor) and where the liquid feed / diluent / hydrogen mixture is passed through the catalyst.
    [040] Surprisingly, the process of the present invention eliminates or minimizes coking the catalyst, which is one of the biggest problems with conventional hydrocarbon feeds, as defined herein. Since high hydrogen absorption in the hydrotreating of heavy feeds (for example, from 100 to 530 L / L, from 560 to 3,000 scf / bbl) results in high heat generation in the reactor, severe cracking is expected to occur at the catalyst surface. If the amount of hydrogen available for the catalyst is not sufficient, cracking can cause the formation of coke and deactivation of the catalyst. The process of the present invention makes available all the hydrogen necessary for the reaction in the liquid feed / diluent / hydrogen mixture, therefore eliminating the need to circulate the hydrogen gas inside the reactor. Since there is enough hydrogen available in the solution, coking the catalyst is largely avoided. In addition, the total liquid reactors of the present invention dissipate heat much better than conventional leaky bed reactors, also contributing to a longer catalyst life.
    [041] The first catalyst is a hydrotreating catalyst and comprises a metal and oxide support. The metal is a non-noble metal selected from the group consisting of nickel and cobalt, and their combinations are preferably combined with molybdenum and / or tungsten. The first catalyst support is a mono- or mixed metal oxide, preferably selected from the group consisting of alumina, silica, titania, zirconia, diatomite, silica-alumina and combinations of two or more of these. Most preferably, the first catalyst support is alumina.
    [042] The second catalyst is a ring opening catalyst and also comprises a metal and oxide support. The metal is also a non-noble metal selected from the group consisting of nickel and cobalt, and their respective combinations, preferably combined with molybdenum and / or tungsten. The second catalyst is a support of zeolite, or amorphous silica, or a combination of these.
    [043] Preferably, the metal for the first catalyst and the second catalyst is a combination of the metals selected from the group consisting of nickel-molybdenum (NiMo), cobalt-molybdenum (CoMo), nickel-tungsten (NiW) and cobalt-tungsten (CoW).
    [044] The first and second catalysts can still comprise other materials that include carbon, such as activated carbon, graphite and carbon nanotube, as well as calcium carbonate, calcium silicate and barium sulfate.
    [045] Preferably, the first catalyst and the second catalyst are in the form of particles, more preferably molded particles. By "molded particle" is meant that the catalyst is in the form of an extrudate. Extruded products include cylinders, pellets and spheres. Cylindrical shapes may have hollow interiors with one or more reinforcement ribs. Molded trilobular tubes, shamrock leaves, rectangular and triangular, and catalysts molded in a “C” shape and transversal can be used. Preferably, the molded catalyst particle is about 0.25 to about 13 mm (about 0.01 to about 0.5 inches) in diameter when a packaged bed reactor is used. Most preferably, the catalyst particle is about 0.79 to about 6.4 mm (about 1/32 to about 1/4 inch) in diameter. These catalysts are commercially available.
    [046] Catalysts can be sulphidized before and / or during use by contacting the catalyst with a sulfur-containing compound at an elevated temperature. Suitable sulfur-containing compounds include thiols, sulfides, disulfides, H2S, or combinations of two or more of these. The catalyst can be sulphidized before use (“pre-sulphide”) or during the hydrotreating process (“sulphide”) by introducing a small amount of a sulfur-containing compound into the feed of heavy hydrocarbons or diluent. The catalysts can be pre-sulphide in situ or ex situ and the feed or diluent can be supplemented periodically with the compound containing the added sulfur to keep the catalyst in a sulphidized condition. The Examples provide a pre-sulphide procedure. BRIEF DESCRIPTION OF THE FIGURES
    [047] Figure 1 provides an illustration of an embodiment of the hydrocarbon conversion process of the present invention. Certain detailed characteristics of the proposed process, such as pumps and compressors, separation equipment, feed tanks, heat exchangers, product recovery containers and other auxiliary process equipment are not shown for the sake of simplicity and to demonstrate the main characteristics of the process. Such auxiliary characteristics will be appreciated by a technician of the subject. It is still preferable that such auxiliary and secondary equipment can be easily designed and used by a person skilled in the art, without any difficulty or any undue experimentation or invention.
    [048] Figure 1 illustrates an exemplary integrated hydrocarbon processing unit (1). The fresh supply of hydrocarbons, such as a light cycle oil or a heavy oil, is introduced through the line (3), and combined with a part of the effluent from the bed (55) (bed (4)) through the line ( 19) at the mixing point (2). The part of the effluent in the line (19) is pumped through the pump (60) to the mixing point (2) to provide the combined liquid feed (4). A stream of hydrogen gas is mixed with the combined liquid feed (4) through the line (6) at the mixing point (5) to introduce enough hydrogen to saturate the combined liquid feed (4). The resulting combined liquid feed / hydrogen mixture flows through the line (7) in the first pre-treatment bed (25) (bed (1)).
    [049] The main source of hydrogen (17) is the source for constituting hydrogen for the first three beds (bed (1), bed (2) and bed (3)).
    [050] The effluent from the pre-treatment bed (25), line (8) is mixed with the additional fresh hydrogen gas fed through the line (9) at the mixing point (10) and the substantially combined liquid flow flows through the line (11) to the second pre-treatment bed (35) (bed (2)). The pretreatment effluent leaves the pretreatment bed (35) through the line (12). The pre-treated effluent in the line (12) is combined with the additional fresh gaseous hydrogen fed through the line (13), at the mixing point (14) to provide a liquid feed. The liquid mixing point feed (14) is fed through the line (15) and the first ring opening bed (45) (bed (3)). The effluent from the first ring opening bed (45) is fed to the second ring opening bed (55) (reactor 4) through the line (16). The effluent from the ring opening bed (55) is removed through the line (18). A part of the effluent from the line (18) returns to the first pre-treatment bed (25) through the line (19), through the pump (60) to the mixing point (2). The proportion of the fresh hydrocarbon feed fed through the line (3) to the effluent from the line (19) is preferably between 1 and 8. The effluent from the line (18) is sent through the line (20 ) to control the valve (70). From the control valve (70), the effluent is fed through the line (21) to the separator (80). The gas products are removed via the line (22). The total liquid product is removed via the line (23). The product from line (23) can be fractionated (distilled) elsewhere to separate a smaller naphtha mix (gasoline) stock from a substantially higher amount of a diesel mix stock.
    [051] The liquid flow (feed, diluent, including the recycle product flow, and hydrogen) in Figure 1 is illustrated as the downward flow through Reactors 1 to 4. It is preferable that the feed / diluent / hydrogen mixture and the product effluents are fed to the reactors in a downward flow mode. However, an upward flow process is also contemplated in the present. EXAMPLES ANALYTICAL METHODS AND TERMS
    [052] ASTM standards. All ASTM Standards are available from ASTM International, West Conshohocken, PA, www.astm.org.
    [053] The amounts of sulfur, nitrogen and nitrogen-based are given in parts per million by weight, wppm.
    [054] Total sulfur was measured using ASTM D4294 (2008), “Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry“, DOI: 10.1520 / D4294-08 and ASTM D7220 (2006 ), “Standard Test Method for Sulfur in Automotive Fuels by Polarization X-ray Fluorescence Spectrometry”, DOI: 10.1520 / D7220-06
    [055] Total nitrogen was measured using ASTM D4629 (2007), “Standard Test Method for Trace Nitrogen in Liquid Petroleum Hydrocarbons by Syringe / Inlet Oxidative Combustion and Chemiluminescence Detection”, DOI: 10.1520 / D4629-07 and ASTM D5762 (2005), ”Standard Test Method for Nitrogen in Petroleum and Petroleum Products by Boat-Inlet Chemiluminescence”, DOI: 10.1520 / D5762-05.
    [056] The aromatic content was determined using ASTM D5186-03 (2009), “Standard Test Method for Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel Fuels and Aviation Turbine Fuels by Supercritical Fluid Chromatography”, DOI: 10.1520 / D5186 -03R09.
    [057] The boiling point distribution (Table 1) was determined using ASTM D6352 (2004), “Standard Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range from 174 to 700 ° C by Gas Chromatography ', DOI : 10.1520 / D6352-04R09.
    [058] The distribution of the boiling range (Tables 4 and 7) was determined using the ASTM D2887 (2008) standard, “Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography,” DOI: 10.1520 / D2887-08.
    [059] The density, specific gravity and API gravity were determined using the standard ASTM D4052 (2005), “Standard Test Method for Density, Relative Density, and API Gravity of Liquids by Digital Density Meter”, ASTM International, West Conshohocken, PA, 2003, DOI: 10.1520 / D4052-09.
    [060] The term “API gravity” refers to the gravity of the American Petroleum Institute, which is a measure of the weight or lightness of a petroleum liquid compared to water. If the API gravity of a petroleum liquid is greater than 10, it is lighter than water and floats if it is less than 10, it is heavier than water and sinks. API gravity, therefore, is an inverse measure of the relative density of a petroleum liquid and the density of water, and is used to compare the relative densities of petroleum liquids.
    [061] The formula for obtaining the API gravity of petroleum liquids from specific gravity (SG) is: API gravity = (141.5 / SG) - 131.5 The number of bromine is a measure of the aliphatic unsaturation in the samples of oil. The bromine number was determined using the standard D1 ASTM 159, 2007, “Standard Test Method for Bromine Numbers of Petroleum Distillates and Commercial Aliphatic Olefins by Electrometric Titration,” DOI: 10.1520 / D1 159-07.
    [062] The Cetane Index is useful for estimating the number of cetane (a measure of the combustion quality of a diesel fuel), when a test engine is not available or if the sample size is too small to determine that property directly . The Cetane Index was determined using the standard ASTM D4737 (2009a), “Standard Test Method for Calculated Cetane Index by Four Variable Equation,”, DOI: 10.1520 / D4737-09a.
    [063] The cloud point is an index of the lower temperature of the usefulness of an oil product for certain applications. The cloud point was determined by the standard ASTM D2500 - 09 “Standard Test Method for Cloud Point of Petroleum Products”, DOI: 10.1520 / D2500-09.
    [064] The term “LHSV” means a net space velocity per hour, which is the volumetric rate of the liquid feed, divided by the volume of the catalyst, and is given in hr-1.
    [065] The Refractive Index (IR) was determined using the standard ASTM D1218 (2007), “Standard Test Method for Refractive Index and Refractive Dispersion of Hydrocarbon Liquids,” DOI: 10.1520 / D1218-02R07.
    [066] The term “WABT” means the weighted average bed temperature.
    [067] The following Examples are presented to illustrate the specific embodiments of the present invention and should not be considered in any way as limiting the scope of the present invention. EXAMPLES 1 TO 3
    [068] The properties of a diesel (GO) from a commercial refiner are shown in Table 1. The GO was hydroprocessed in an experimental pilot unit that contains a set of three series fixed bed reactors. Each reactor was made of a 19 mm (% ”) OD 316L stainless steel tube and about 61 cm (24”) in length, with 6 mm (% ”) reducers at each end. Both ends of the reactors were first covered with a metal mesh to prevent leakage of the catalyst. Below the metal mesh, the reactors were packed with layers of glass beads of 1 mm at both ends. The catalyst was packaged for the middle section of the reactor. TABLE 1 PROPERTIES OF DIESEL USED IN EXAMPLES 1 AND 13

    [069] The first two reactors, Reactors 1 and 2, were used for the target pretreatment (“PT”). Reactors 1 and 2 contained a hydrotreatment catalyst for hydrodenitrogenation (HDN), hydrodesulfurization (HDS) and hydrodearomatization (HDA). About 48.6 ml and 90 ml of catalyst were loaded into the first and second reactors, respectively. The catalyst, KF-860, was a NiMo on Y-AI2O3 support from Albemarle Corporation, Baton Rouge, LA. It was in the form of extrusions of a quadralobe of about 1.3 mm in diameter and 10 mm in length. Reactor 1 was packaged with layers of 30 ml (bottom) and 25 ml (top) of glass beads, while Reactor 2 was packaged with a layer of 10 ml (bottom) and 9 ml (top) of glass beads.
    [070] Reactors 3 and 4 were used for the selective opening of the ring (“RO”). Reactors 3 and 4 were packed with layers of glass beads of 1 mm at both ends, 10 mL at the bottom and 15 mL at the top, and contained 90 mL of each selective ring opening catalyst. This catalyst, KC-2610, was a NiW catalyst on an Albemarle zeolite support. It was in the form of an extrudate of a cylindrical shape about 1 mm in diameter and 1.5 mm in length.
    [071] Each reactor was placed in a temperature-controlled sand bath in a 7.6 cm (3 ”) OD tube and 120 cm long filled with fine sand. The temperature was monitored at the entrance and exit of each reactor, as well as in each sand bath. The temperature in each reactor was controlled using the heat tapes wrapped around the 7.6 cm (3 ”) DO tube and connected to the temperature controllers. After leaving Reactor 4, the effluent was divided into a recycling stream and a product effluent. The liquid recycling stream flowed through a piston metering pump to join a fresh supply of hydrocarbons at the inlet of the first reactor.
    [072] Hydrogen was fed from the compressed gas cylinders and flow rates were measured using mass flow controllers. The hydrogen was injected and mixed with the combined GO fresh feed and the recycle product flow, before Reactor 1. The flow of the combined “GO fresh product / hydrogen / recycle” flowed downwards through a first bath. temperature controlled sand in a 6 mm OD pipe and then in an upward flow mode through Reactor 1. After leaving Reactor 1, additional hydrogen was injected into the effluent from Reactor 1 (feed to the Reactor 2). Feed for Reactor 2 flowed downward through a second temperature-controlled sand bath in a 6 mm OD pipe and then in an upward flow mode through Reactor 2. After leaving Reactor 2, more hydrogen was dissolved in the effluent from Reactor 2 (feed to Reactor 3). The liquid feed for Reactors 3 and 4 followed the same pattern, with injection of hydrogen gas before each reactor.
    [073] In Example 1, the target pretreatment catalyst (total 138.6 mL) and the selective ring opening catalyst (total 180 mL) were loaded into the reactors as described above. They were dried overnight at 115 ° C under a total flow of 300 standard cubic centimeters per minute (sccm) of hydrogen. The pressure was 6.9 MPa (69 bar). The charged catalyst reactors were heated to 176 ° C with a lighter fluid flow of coal through the catalyst beds. The sulfur-fortifying agent (1% by weight of sulfur, added as 1-dodecanethiol) and hydrogen gas were introduced into the lighter coal fluid at 176 ° C to pre-sulphide the catalysts. The pressure was 6.9 MPa (69 bar). The temperature of the reactors was gradually increased to 320 ° C (610 ° F). The pre-sulphide was continued at 320 ° C, until the rupture of the hydrogen sulfide (H2S) was observed at the outlet of the Reactor 4. After the pre-sulphide, the catalyst was stabilized by flowing a supply of a linearly running diesel (SRD) ) through the catalyst beds, at a temperature ranging from 320 ° C to 355 ° C and at 6.9 ° MPa (1,000 psig or 69 bar) for about 10 hours.
    [074] After pre-sulphide and stabilization of the catalyst, the GO feed mixture was preheated to 50 ° C, and was pumped to Reactor 1 using a syringe pump at a flow rate of 2.25 mL / minute, for a 1.0 hr-1 LHSV pretreatment. The total hydrogen feed rate was 180 normal liters per liter (NL / L) of the fresh hydrocarbon feed (1,000 scf / bbl). Reactors 1 and 2, had a weighted average bed temperature or WABT of 382 ° C. Reactors 3 and 4, were kept under 204 ° C to initially avoid any reaction of the selective ring opening. The pressure was 10.8 MPa (108 bar). The recycling rate was 5. The pilot unit was maintained in these conditions for an additional 10 hours to ensure that the catalyst was fully pre-coked and the system was aligned during testing of product samples, for total sulfur and total nitrogen. . The results are given in Table 2. TABLE 2 SUMMARY OF EXAMPLES 1 TO 3

    [075] Abbreviations: TP is the pre-treatment target for the removal of nitrogen, sulfur and aromatics.
    [076] RO is the selective opening of the ring to break the larger hydrocarbon molecules into smaller hydrocarbon molecules.
    [077] RR is the proportion of recycling.
    [078] BP a (50%) is the boiling point at 50% of the mixture, as determined by the ASTM D6352 standard.
    [079] The tests of Examples 2 and 3 were conducted under conditions similar to those of Example 1. Example 2 was run on a 393 ° C WABT using Reactors 1 and 2 only at the recycling rate of 6.9. Example 3 was run on a 393 ° C WABT using Reactors 1 to 4 (both PT and RO) at the recycling rate of 5. The results are shown in Table 2.
    [080] A sample of the Total Net Product (TLP) and a sample of the exhaust gas were collected for each Example under steady state conditions. The sulfur and nitrogen contents for the products of Example 1 and Example 2, none involved ring opening, were low enough to not pose a risk of poisoning a ring opening catalyst based on zeolite. The conversion of the selective ring opening (based on the average boiling point) for Example 3 was about 32%. These results show that the combined target pretreatment and the selective ring opening process reduces the feed density much more than the use of a single target pretreatment process. EXAMPLES 4 TO 8
    [081] A 100% light cycle oil (LCO) from an oil refinery's FCC unit, which has the properties described in Tables 3 and 4, has been hydroprocessed in the pilot unit described in Example 1, with certain changes . TABLE 3 LIGHT CYCLE OIL PROPERTIES USED IN EXAMPLES 4 TO 8
    TABLE 4 DISTRIBUTION OF Leo'S BOILING POINT USED IN EXAMPLES 4 TO 8

    [082] Tables 3 and 4 show that, compared to a diesel sample, the LCO feed has a higher boil with a polyaromatic content of 45.6% by weight and higher density. The “Preferred Diesel Specimens” column in Table 3 provides the corresponding values of the preferred properties for the diesel product - a cetane number of at least 12 points higher than that of the feed, and a density not exceeding 0.860 g / mL at 15.6 ° C. Other preferred properties not listed in Table 3 include a minimum freezing point of -10 ° C and a minimum flash point of 62 ° C.
    [083] Four reactors were used in these Examples. The reactors were packaged with the catalysts as described in Example 1. Reactors 1 and 2 each contained 60 mL, a commercial NiMo in the catalyst Y-AI2O3 (TK-607) for pretreatment. Reactors 3 and 4 each contained 60 mL of a commercial NiW catalyst in alumina / zeolite (TK-951) for selective ring opening. Both catalysts are available from Haldor Tops0e, Lyngby, Denmark.
    [084] For each of Examples 4 through 8, the catalysts were dried and pre-sulphidized as described in Example 1 with the exception that the final temperature of the pre-sulphide period was 349 ° C for the pretreatment catalyst target (TK-607) and 371 ° C for the selective ring opening catalyst (TK-951). After pre-sulphide, the feed was changed to SRD to stabilize the catalyst, as described in Example 1, at a constant temperature of 349 ° C and a pressure of 6.9 MPa (69 bar) for 12 hours in one step of initial pre-coking. The feed was then transferred to the CSO in order to complete the pre-coking of the catalysts through the CSO feed for at least 6 hours and through the sulfur test until the system is in a steady state.
    [085] The LCO feed was preheated to 93 ° C and pumped to Reactor 1. Certain run conditions (feed rate - LHSV, Reactor temperatures - WABT) are provided in Table 5. Other conditions are like follow. The feed rate for total hydrogen was 356 L / L (2,000 scf / bbl). The pressure was 13.8 MPa (138 bar). The recycling rate was 6. The unit was run for 6 hours to achieve the steady state.
    [086] TLP samples collected at the end of Reactor 4, under steady state conditions, were batch distilled to remove the cut of naphtha (maximum boiling point of 200 ° C) and a cut of diesel from the remaining liquid product . The results for Examples 4 through 8 are shown in Table 5.
    [087] As can be seen in Table 5, hydrogen consumption was extremely high, in all Examples that exceed 250 normal liters of H2 per liter of oil, N L / L (1,400 scf / bbl). This is surprisingly high compared to the consumption rates normally seen in ULSD applications ranging from 35 to 73 NL / L (from 200 to 400 scf / bbl) by Parkash, S, Refining Processes Handbook (page 48) Elsevier, 2003 ). After the reaction, the catalysts in Examples 4 to 8 showed no evidence of short-term coking.
    [088] Sulfur and nitrogen contents were found to be at preferred levels of diesel products from this pretreatment / ring opening process. In the most severe conditions, in Examples 4 and 5 (upper WABT, lower LHSV), diesel products meet the preferred specifications for diesel. The feed density has been reduced by up to 8.5% and the cetane number has been substantially increased. Naphtha yield was less than 23% on a weight basis.
    [089] The results for Examples 4 to 8 demonstrate the ability of the combined hydrotreating / ring-opening process in several reactors to improve the LCO for available flows with the acceptable properties for diesel to be mixed in the diesel tank in one oil refinery. TABLE 5 SUMMARY OF EXAMPLES 4 TO 8
    EXAMPLES 9 TO 13
    [090] Two LCO feeds from an FCC unit were hydroprocessed in the same pilot unit described in Examples 1 through 8. The properties of these feeds are given in Tables 6 and 7. LCO1 was used in Examples 9 and 10, and had properties very similar to those used in Examples 4 to 8. LCO2 was used in Examples 11 to13 and was a slightly lighter diet than LCO1 with about 1/3 of the sulfur content and a similar nitrogen content . The total content of aromatics and polyaromatics in LCO2 was about 2% by weight higher than that of LCO1. TABLE 6 LCO FOOD PROPERTIES USED IN EXAMPLES 9 TO 13

    TABLE 7 DISTRIBUTION OF THE BOILING POINT OF LCO FOODS FOR EXAMPLES 9 TO 13

    [091] The process of Examples 4 to 8 was repeated using four reactors. Reactors 1 and 2 contained a target pretreatment catalyst, KF-860, NiMo in the alumina support, while Reactors 3 and 4 contained the ring opening catalyst, KC-2610, NiW in zeolite. Both catalysts were obtained from Albemarle Corporation, Baton Rouge, LA. The catalysts were loaded, dried, sulphidized and stabilized with the SRD, as described in Example 1.
    [092] In Example 9, after pre-sulphide and stabilization of the catalyst with a diesel pressure range of SRD (6.9 MPa), the LCO2 feed was pumped to Reactor 1 using a positive displacement pump at 2 , 5 ml / minute. The reaction variables for Examples 9 through 13 are provided in Table 8. The total hydrogen feed rate for these Examples was 382 L / L (2,143 scf / bbl). The pressure was 138 bar (13.8 MPa). The unit was run for 5 hours before collecting samples to achieve the steady state. For clarity, in the fourth column of Table 8 (WABT), the first number represents the temperature of Reactors 1 and 2, and the second number represents the temperature of Reactors 3 and 4. TABLE 8 SUMMARY OF EXAMPLES 9 TO 13

    [093] Samples were collected on a permanent basis. The TLP samples were batch distilled to remove the naphtha product (maximum boiling point of 200 ° C) from the diesel product. Table 8 provides the results for TLP and diesel products.
    [094] Compared to food, product samples in Examples 9 to 13 show significantly reduced density and lower levels of sulfur and nitrogen, hydrogen consumption was greater than 330 N L / L (1,900 scf / bbl). The cetane number increased by more than 12 points in the diesel products of all samples in Examples 9 through 13. Monoaromatics and polyaromatics were less than 31 and 7% by weight, respectively, for the diesel products of Examples 9 to 11. The cloud point and flash point in the diesel product for Example 9 were found to be from 10 ° C to 80 ° C, respectively. Therefore, the target pretreatment / selective ring opening process can be used to improve the LCO for higher value products that can be used as the mixture stock for diesel fuel. EXAMPLES 14 TO 21
    [095] The LCO2 supply described in Examples 9 to 13 was handled in the pilot unit described in Example 1.
    [096] Reactors 1 and 2 contained the target pretreatment catalyst, KF-860, while Reactors 3 and 4 contained the selective ring opening catalyst, KC-3210, the two catalysts are from Albemarle. The catalysts were loaded, dried, sulphidized and stabilized, as described in Example 1.
    [097] After pre-sulphide and stabilization of the catalyst, the LCO2 feed was pumped to Reactor 1 using a positive displacement pump at 2.5 mL / minute. The salient variables are provided in Table 9. For clarity, in the fourth column of Table 9 (VABT), the first number represents the temperature of Reactors 1 and 2, and the second number represents the temperature of Reactors 3 and 4. The total rate hydrogen feed was 325 L / L (1,829 scf / bbl). The pressure was 138 bar (13.8 Pa). The pilot unit was kept in the reaction conditions for 5 hours to reach the steady state before collecting any samples. TABLE 9 SUMMARY OF EXAMPLES 14 TO 21


    [098] The results for Examples 14 to 21 are shown in Table 9. TLP samples were collected and distilled in batch to remove the naphtha product (maximum boiling point 200 ° C) from the diesel product . The properties of the diesel product are shown in Table 9. The naphtha product varied from 10 to 15% by weight.
    [099] The results demonstrate that the process can be used to improve the LCO for higher value flows. As can be seen from Table 9, while sulfur and nitrogen were reduced, the reduction in density did not reach the preferred level of 860 g / mL and the cetane number was only moderately increased, suggesting a lower ring opening than preferred. The naphtha product, however, was only 10 to 15%. The total hydrogen consumption was 270 L / L (1,517 scf / bbl), lower than that achieved in Examples 11 to 13. The relatively low increase in the cetane index values (compared to the feed) indicates a lower opening activity of the ring. Therefore, while improvements in the properties of the treated LCO were observed again, the selection of the selective ring opening catalyst affects the quantities and properties of the naphtha and diesel products. If a modest increase in the cetane number from a modest reduction in density is acceptable, the ring opening catalyst used in Examples 14 through 21 would convert 85 to 90% of the LCO feeds into diesel product. EXAMPLES 22 TO 25
    [0100] The LCO2 feed used in Examples 9 and 10 was used in the present. The pilot unit e was the same as described in Example 1. The properties of the feeds are shown in Tables 6 and 7. The process of Examples 9 to 13 was repeated using four reactors. Reactors 1 and 2 contained the target pretreatment catalyst, KF-860, while Reactors 3 and 4 contained the selective ring opening catalyst, KC-2710 (NiW in zeolite, 1.5 mm OD cylinders), the two catalysts are from Albemarle. The catalysts were loaded, dried, sulphidized and stabilized, as described in Example 1.
    [0101] After pre-sulphide and stabilization of the catalyst, the LCO2 feed was pumped to Reactor 1 using a positive displacement pump at 2.5 mL / minute. The variables are provided in Table 9. As in Tables 8 and 9, the fourth column of Table 10 provides the temperature of Reactors 1 and 2 (first number), and the temperature of Reactors 3 and 4 (second number). The total hydrogen feed rate was 325 L / L (1,829 scf / bbl). The pressure was 138 bar (13.8 Pa). The pilot unit was maintained in the reaction conditions for 5 hours to reach the steady state before collecting any samples. TABLE 10 SUMMARY OF EXAMPLES 22 TO 25


    [0102] The results for Examples 22 to 25 are shown in Table 10. The TLP samples were batch distilled to remove the cut of the naphtha product (maximum boiling point of 200 ° C) from the cut of the diesel product . The naphtha product was superior in the TLP samples of Examples 22 to 25 (reaching a maximum of 40%) than those obtained in Examples 9 to 13, suggesting a superior selective ring opening activity with the KC-2710 catalyst used at present that that observed with the catalyst KC-2610 used in Examples 9 to 13. The naphtha products in the TLP samples of Examples 22 to 25 were much superior to those obtained in Examples 14 to 21 (naphtha product of about 10 to 15%).
    [0103] These results show that it is possible to obtain a higher reduction in density, a higher increase in the cetane index, but that the performance comes with the increase in the production of naphtha, which reduces the yield of the diesel product. Therefore, the distribution of the products (naphtha and diesel products) and the product properties can be changed with the reaction conditions, such as temperature, pressure, feed flow rate (LSHV), and / or recycling. COMPARATIVE EXAMPLES
    [0104] Comparative Examples were conducted only with the target pretreatment catalysts (free of selective ring opening catalyst). Comparative Examples illustrate the value and importance of the combined two-step process proposed in the present invention. Before performing the Comparative Examples, it was determined that one stage could only achieve a small degree of reduction of sulfur, nitrogen and aromatics, and that at least two stages of the total liquid reactors, as defined herein, were required. Two pre-treatment stages were used in these Examples. COMPARATIVE EXAMPLES FROM A TO I
    [0105] The LCO feed described in Examples 4 to 8 was used. The properties of the feed are given in Tables 3 and 4.
    [0106] Reactors 1 and 2 were used in this experiment. Except for the following, the reactor conditions are the same as those of Example 4. The reactors were packaged with a target pretreatment catalyst, as described in Example 4. Reactors 1 and 2 each contained 60 mL of a commercial NiMo in the catalyst Y-AI2O3 (TK-607). The drying, pre-sulphide and stabilization of the catalyst were carried out as described in Example 4. The reaction conditions (feed rate - HSV, Reactor temperature - WABT and recycling rate - RR) are provided in Table 11.
    [0107] TLP samples and exhaust gas samples were collected when the reactors reached steady state. As shown in Table 11, the different conditions were explored to study the kinetics of sulfur and nitrogen, as well as to find the ideal conditions for the target pretreatment, before feeding the pretreated product to the opening reaction zone. selective ring. The maximum nitrogen content that can be tolerated through the ring opening catalyst, without deactivation is about 5 ppm to about 50 wppm. As shown in Table 11, the minimum conditions to satisfy the nitrogen content have been achieved in most of the Comparative Examples from A to I. If a process condition that leaves a substantial amount of unreacted organic nitrogen in the product at the exit of the target pretreatment is used for the combined “target pretreatment / selective ring opening” process, the ring opening catalyst would be poisoned.
    [0108] The Comparative Examples from E to H considered whether increasing the severity of the reaction conditions, that is, reducing the LHSV to 1 hr-1 and increasing the temperature would result in satisfying the preferred specifications of the diesel product. Under more severe conditions, (Example E, an LHSV of 1.00 hr-1 and WABT of 371 ° C), the density was reduced to just 0.8827 g / mL and the cetane index increased to 30.4, with a relatively high consumption of hydrogen. TABLE 11 SUMMARY OF COMPARATIVE EXAMPLES OF AAI
    COMPARATIVE EXAMPLES OF JAO
    [0109] The LCO feed used was used in Examples 9 and 10. The properties of this feed are given in Tables 6 and 7.
    [0110] Two reactors were used in this experiment. The reactors were packaged with a target pretreatment catalyst, as described in Example 9. Reactors 1 and 2 each contained 60 ml of a commercial NiMo in the Y-AI2O3 catalyst (from Albemarle KF-860). The drying, pre-sulphide and stabilization of the catalyst were carried out as described in Example 9.
    [0111] TLP samples and exhaust gas samples were collected when the reactors reached steady state. As shown in Table 12, the kinetics of sulfur and nitrogen were studied through variations in the reaction conditions. The conditions for pretreatment before feeding the pretreated product to the ring opening section area were explored. Again, the maximum nitrogen content that can be tolerated through the ring opening catalyst without deactivation is between about 5 ppm and about 50 ppm. As shown in Table 12, the minimum conditions to achieve the target nitrogen content were achieved in Comparative Examples M, N and O, at an LHSV of 1.1-1 and a recycling rate of 4.7. The density of the products under these conditions is not very high in relation to the preferred sulfur specification of the diesel product (0.881 vs 0.860 g / ml). TABLE 12 SUMMARY OF JAO'S COMPARATIVE EXAMPLES

    [0112] Table 13 compares the differences in the selected properties for only the target pretreatment (Comparative Examples from A to O) against the combined target pretreatment and the selective ring opening (Examples 1 to 25). The selected Examples have been selected for illustration. Table 13 shows the reaction conditions, aromatic content, density and cetane number for the diesel products in these selected Examples.
    [0113] The total reduction of aromatics in a combined “target pretreatment / selective ring opening” system with a single recycling circuit differs from the same system with only the target pretreatment. Density reduction is enhanced when the selective ring opening catalyst is used after the target pretreatment. In addition, the cetane number and naphtha yields are higher when the target pretreatment is combined with the selective ring opening. The reduction in density associated with the ring opening catalyst (see Examples 4 and 5 vs Example E in Table 13), indicates that the selective manipulation of the ring is taking place before the saturated (naphthenic) polyaromatic compounds formed in the pre-treatment stage target. Even if the polyaromatic content decreases (compared to food), the monoaromatic content remains the same.
    [0114] In the case of only the target pretreatment (Example E), the most aromatic saturation appears for the formation of naphthenic hydrocarbons. When a selective ring opening catalyst is used after the target pretreatment, the reduction in additional density appears to indicate the opening of the naphthenic rings since the total aromatic content, and the relative amounts of the mono and polyaromatics remain the same ( Examples 4 and 5 vs Example E in Table 13).
    [0115] Comparison of Examples 9 to 13 with Comparative Examples from M to O shows similar behavior. Whereas, the extent of aromatic saturation is lower when the selective ring opening is combined with the target pretreatment, a lower density results when a target pretreatment and the selective ring opening catalysts are used in a single circuit of recycling (Example 9 to 13) versus only the target pretreatment catalyst (Examples from M to O).
    [0116] Consequently, ring manipulation was achieved using the total net reaction system by combining the target pretreatment and the selective ring opening catalysts in a single recycling loop with improvements in density reduction and index increases. of cetane. Such enhancements provide an LCO product that meets the requirements of Euro IV or V diesel and can be mixed in a diesel tank. TABLE 13 COMPARISON OF AROMATIC CONTENT, DENSITY, CETANE INDEX FOR VARIOUS EXAMPLES
    权利要求:
    Claims (24)
    [0001]
    1. PROCESS FOR THE HYDROPROCESSING OF A HYDROCARBON FEED, characterized by comprising: (a) the contact of the hydrocarbon feed that has a density of at least 0.910 g / mL at a temperature of 15.6 ° C, and a boiling point in the range of 375 ° C to 650 ° C, an API gravity in the range of 24 to 0, a sulfur content in the range of 1,500 to 25,000 parts per million by weight (wppm), and a higher nitrogen content at 500 wppm with (i) a diluent and (ii) hydrogen, for the production of a feed / diluent / hydrogen mixture, in which the hydrogen is dissolved in the mixture to provide a liquid feed; (b) the contact of the feed / diluent / hydrogen mixture with a first catalyst in a first treatment zone, for the production of a first product effluent; (c) the contact of the first product effluent with a second catalyst in a second treatment zone, for the production of a second product effluent; and (d) recycling a portion of the second product effluent as a stream of the recycling product for use in the diluent in step (a) (i) at a recycling rate from 1 to 8, without separating the ammonia and hydrogen sulfide and hydrogen remaining from said portion of the product's second effluent, in which the hydrogen is recycled with the flow of the recycling product; where the first treatment zone comprises at least two stages, where the first catalyst is a hydrotreating catalyst and the second catalyst is a ring-opening catalyst, the first and second treatment zones are the zones of the total liquid reaction, and the total amount of hydrogen fed to the process is greater than 100 normal liters of hydrogen per liter of feed, without separating the ammonia and hydrogen sulfide and hydrogen remaining from the first effluent product prior to feeding the first product effluent to the second treatment area.
    [0002]
    PROCESS according to claim 1, characterized in that the hydrocarbon feed is a heavy hydrocarbon or a light cycle oil.
    [0003]
    3. PROCESS, according to claim 1, characterized in that the total amount of hydrogen fed to the process is 200 to 530 L / L (from 1,125 to 3,000 scf / bbl).
    [0004]
    4. PROCESS, according to claim 3, characterized in that the total amount of hydrogen fed to the process is 250 to 360 L / L (from 1,300 to 2,000 scf / bbl).
    [0005]
    PROCESS according to claim 1, characterized in that both the first and second treatment zones have a temperature from 300 ° C to 450 ° C, pressure from 3.45 MPa (34.5 bar) to 17 , 3 MPa (173 bar), and a hydrocarbon feed rate to provide an hourly spatial liquid velocity (LHSV) of 0.1 to 10 hr-1.
    [0006]
    6. PROCESS, according to claim 1, characterized in that both the first and second treatment zones have a temperature from 350 ° C to 400 ° C, pressure from 6.9 MPa (69 bar) to 13.9 MPa (139 bar), and a hydrocarbon feed rate to provide an hourly spatial liquid velocity (LHSV) of 0.4 to 4 hr-1.
    [0007]
    7. PROCESS, according to claim 1, characterized in that the diluent comprises an organic liquid selected from the group consisting of light hydrocarbons, light distillates, naphtha, diesel and combinations of two or more of these.
    [0008]
    PROCESS, according to claim 1, characterized in that the first treatment zone comprises at least two catalyst beds in a reactor, wherein the beds are physically separated by a catalyst-free zone.
    [0009]
    9. PROCESS, according to claim 1, characterized in that the first treatment zone comprises at least two reactors, each reactor containing a catalyst bed and in which the reactors are separated by a catalyst-free zone.
    [0010]
    PROCESS, according to claim 8, characterized in that the reactor comprises both the first treatment zone and the second treatment zone.
    [0011]
    PROCESS according to any one of claims 8 to 10-, characterized in that fresh hydrogen is added between the catalyst beds for the catalyst-free zone.
    [0012]
    12. PROCESS, according to claim 11, characterized by the mixture of feed / diluent / hydrogen and the effluent products being fed from bed to bed in a downward flow mode.
    [0013]
    13. PROCESS, according to claim 11, characterized by the mixture of feed / diluent / hydrogen and the effluent products being fed from bed to bed in an upward flow mode.
    [0014]
    14. PROCESS, according to claim 1, characterized in that the first catalyst comprises a metal and oxide support, in which the metal is selected from the group consisting of nickel and cobalt, and their combinations, combined with molybdenum and / or tungsten, and the oxide support is selected from the group consisting of alumina, silica, titania, zirconia, diatomite, silica-alumina and combinations of two or more of these.
    [0015]
    15. PROCESS, according to claim 14, characterized in that the first catalyst support is alumina.
    [0016]
    16. PROCESS, according to claim 1, characterized in that the second catalyst comprises a metal and oxide support, in which the metal is selected from the group consisting of nickel and cobalt, and their combinations, combined with molybdenum and / or tungsten, and the oxide support is a zeolite, amorphous silica, or a combination of these.
    [0017]
    17. PROCESS, according to claim 1, characterized in that the first and the second catalysts each comprise a metal that is a combination of the metals selected from the group consisting of nickel-molybdenum (NiMo), cobalt-molybdenum ( CoMo), nickel-tungsten (NiW) and cobalt-tungsten (CoW).
    [0018]
    18. PROCESS according to claim 1, characterized in that the first and second catalysts are sulphidized.
    [0019]
    19. PROCESS according to claim 1, characterized in that the liquid portion of the second product effluent comprises less than 50% by weight of naphtha product and less than 50% by weight of diesel product.
    [0020]
    20. PROCESS according to claim 1, characterized in that the liquid portion of the second product effluent comprises less than 25% by weight of naphtha product and less than 75% by weight of diesel product.
    [0021]
    21. PROCESS according to any one of claims 19 to 20, characterized in that the diesel product has a sulfur content of less than 50 wppm and a nitrogen content of less than 10 wppm.
    [0022]
    22. PROCESS according to any one of claims 19 to 20, characterized in that the diesel product has a cetane number increased by at least 12 points in relation to the hydrocarbon feed.
    [0023]
    23. PROCESS, according to any one of claims 19 to 20, characterized in that the diesel product has a density of about 0.860 g / mL at a temperature of 15.6 ° C, a sulfur content below 50 wppm, and an index of cetane increased by at least 12 points in relation to the hydrocarbon feed.
    [0024]
    24. PROCESS, according to claim 1, characterized by the effluent products having a nitrogen content of less than 50 wppm.
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    同族专利:
    公开号 | 公开日
    US20120205285A1|2012-08-16|
    BR112013018931A2|2016-10-04|
    US9139782B2|2015-09-22|
    RU2593758C2|2016-08-10|
    CN103347987B|2016-08-10|
    JP2014505159A|2014-02-27|
    RU2013141535A|2015-03-20|
    AR085356A1|2013-09-25|
    KR20140020902A|2014-02-19|
    CA2825775A1|2012-08-16|
    SA115360463B1|2016-05-19|
    TW201241168A|2012-10-16|
    SG192005A1|2013-08-30|
    CA2825775C|2020-07-07|
    EP2673341A2|2013-12-18|
    WO2012109649A2|2012-08-16|
    WO2012109649A3|2013-01-24|
    MX2013009120A|2013-11-01|
    KR101923752B1|2018-11-29|
    CN103347987A|2013-10-09|
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    法律状态:
    2019-02-05| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-04-09| B07B| Technical examination (opinion): publication cancelled [chapter 7.2 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 7.1 NA RPI NO 2509 DE 05/02/2019 POR TER SIDO INDEVIDA. |
    2019-07-02| B09B| Patent application refused [chapter 9.2 patent gazette]|
    2019-07-16| B09S| Decision of refusal: publication cancelled [chapter 9.2.2 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 9.2 NA RPI NO 2530 DE 02/07/2019 POR TER SIDO INDEVIDA. |
    2019-07-23| B07C| Technical examination (opinion): republication [chapter 7.3 patent gazette]|Free format text: RETIFICO O PARECER POR INCORRECOES DEVIDO AO USO DE PETICAO DIVERSA. |
    2020-12-01| B25A| Requested transfer of rights approved|Owner name: DUPONT INDUSTRIAL BIOSCIENCES USA, LLC (US) |
    2020-12-22| B25A| Requested transfer of rights approved|Owner name: REFINING TECHNOLOGY SOLUTIONS, LLC (US) |
    2021-01-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-09| B09W| Correction of the decision to grant [chapter 9.1.4 patent gazette]|Free format text: REPUBLIQUE-SE, POR INCORRECAO NO NOME DA DEPOSITANTE |
    2021-03-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/025,427|2011-02-11|
    US13/025,427|US9139782B2|2011-02-11|2011-02-11|Targeted pretreatment and selective ring opening in liquid-full reactors|
    PCT/US2012/024863|WO2012109649A2|2011-02-11|2012-02-13|Targeted pretreatment and selective ring opening in liquid-full reactors|
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