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    • 专利摘要:
    hydroprocessing catalytic composition containing a polar heterocyclic compound, method of manufacturing such composition and process for hydrotreating a hydrocarbon feedstock. a composition comprising a support material which has a metal component incorporated therein and impregnated with an additive compound which is selected from the group of polar, heterocyclic compounds of the formula cxhnnyoz; where: x is an integer of at least 3; y is 0, 1, 2 or 3; z is 0, 1, 2 or 3; and n is the number of hydrogen atoms required to fill the remaining bonds with the carbon atoms of the molecule. the composition includes the support material which is impregnated with the additive compound and is useful in the hydroprocessing of hydrocarbon feedstocks, especially in the denitrogenation and desulfurization of the distillate feedstocks to make ultra-low sulfur diesel.
    公开号:BR112015029993B1
    申请号:R112015029993-8
    申请日:2014-05-29
    公开日:2021-08-31
    发明作者:John Anthony Smegal；Alexei Grigorievich Gabrielov；Ed GANJA；Theofiel Meuris
    申请人:Shell Internationale Research Maatschappij B.V.；
    IPC主号:
    专利说明:

    [001] This application claims the benefit of US Provisional Patent Application No. 61/829689, filed on May 31, 2013.
    [002] This invention relates to a hydroprocessing catalytic composition that includes a heterocyclic compound, in addition to its support material and metallic components, to a method of manufacturing such a hydroprocessing catalytic composition, and its use in catalytic hydroprocessing hydrocarbon raw materials.
    [003] As a result of the very low sulfur concentration specifications for diesel engine fuels, there has been a great deal of effort by those in the industry to find new hydrotreating catalyst formulations and products that can be used in diesel manufacturing with low-frequency and other products.
    [004] A catalyst taught by the art for use in hydrotreating certain hydrocarbon feedstocks to meet some of the more stringent sulfur regulations is disclosed in U.S. Patent No. 5338717. In that patent, a hydrotreating catalyst is disclosed, which is done by impregnating a Group VI heteropolyacid (Mo and/or W) onto a support followed by treating the impregnated support with an aqueous solution of a drying agent which can be dried and thereafter impregnated with a Group VIII metal (Co and/or Ni) salt of an acid that has an acidity less than that of the Group VI heteropolyacid. This impregnated support is then dried and sulfurized to provide a final catalyst.
    [005] The catalytic composition disclosed in the '717 patent can also be made by impregnating a support with either the Group VIII metal metal salt or the Group VI heteropolyacid followed by drying and then treatment with a reducing agent, drying again, and sulphurizing to form the final catalyst.
    [006] Another catalyst useful in deep hydrodesulfurization and other methods of hydrotreating hydrocarbon feedstocks and a method of making such a catalyst and activating it are disclosed in U.S. Patent No. 6872678. The catalyst of the '678 patent includes a carrier whereby a Group VIB metal hydrogenation component and/or a Group VIII metal hydrogenation component and a sulfur-containing organic compound additive are incorporated while still in contact with a fraction organic liquid. Petroleum. The catalyst is treated with hydrogen, either simultaneously with or after incorporation of the organic liquid (petroleum fraction).
    U.S. Patent No. 8262905 discloses a composition which is particularly useful in the catalytic hydroprocessing of hydrocarbon feedstocks. A composition disclosed in the '905 patent includes a support material that is loaded with either an active metal precursor or a metallic component of a metal salt, and hydrocarbon oil and a polar additive. The polar additive has a dipole moment of at least 0.45 and the weight ratio of hydrocarbon oil to polar additive in the composition is in the 10:1 upward range. This is particularly desirable for the polar additive to be a heterocompound, except those heterocompounds that include sulfur. The most preferred polar additive compounds are selected from the group of amide compounds.
    U.S. Patent No. 6540908 discloses a process for preparing a sulfur hydrotreating catalyst. This process involves combining an alumina catalyst carrier and a hydrogenation metal catalyst carrier with an organic compound that includes a covalently bonded nitrogen atom and a carbonyl moiety by sulphiding the resulting combination. The '908 patent does not explicitly teach or exemplify that its organic compound may include a heterocyclic compound. A preferred organic compound is indicated to be one that satisfies the formula (R1R2)N-R3-N(R1'R2').
    [009] There is a continuing need to find improved higher activity hydrotreating catalysts. There is also a need to find more economical manufacturing methods and improved methods of activating the hydrotreating catalysts in order to provide catalysts that have better activity than catalysts activated by the alternative methods.
    [010] Consequently, a catalytic composition is provided which comprises a support material that is loaded with an active metal precursor and a heterocyclic additive. In another embodiment of the invention, the catalytic composition comprises a support material which contains a metallic component of a metal salt solution and a heterocyclic additive.
    [011] The inventive catalyst composition can be made by one of several embodiments of the inventive preparation method. Such an embodiment comprises incorporating a metal-containing solution into a support material to provide a support material incorporated into the metal; and incorporating a heterocyclic additive into the metal-incorporated support material to thereby provide an additive-impregnated composition.
    [012] The catalytic composition of the invention is particularly useful in the hydroprocessing of hydrocarbon feedstocks and can be used in an inventive contact hydrotreating process under the appropriate conditions of hydrotreating process of hydrocarbon feedstock with the catalytic composition to produce a treated product.
    [013] Figure 1 shows a relative volume hydrodesulfurization (HDS) activity to produce an ultra-low sulfur diesel product, that is, a diesel product that has a sulfur content of 10 ppmp, under two different reaction conditions , but at very low pressure, for an inventive Co/Mo catalyst composition and a comparative Co/Mo catalyst composition.
    [014] Figure 2 shows the relative volume deep hydrodenitrogenation (HDN) activity, that is, to produce a diesel product that has a nitrogen content of 5 ppm, under very low pressure reaction conditions for a composition Co/Mo catalyst invention and a comparative Co/Mo catalyst composition.
    [015] Figure 3 shows a relative volume hydrodesulfurization (HDS) activity to produce an ultra-low sulfur diesel product under two different low to moderate pressure reaction conditions for several different stacked catalyst bed reactor (CS1) systems , CS2, CS3) and for a single catalyst bed reactor system (CS4).
    [016] Figure 4 shows the relative hydrogen consumption under the two low to moderate pressure reaction conditions for the stacked catalyst bed reactor and single catalyst bed reactor systems of Figure 3.
    [017] Figure 5 shows the relative volume deep hydrodenitrogenation (HDN) activity to produce a diesel product under two different low to moderate pressure reaction conditions for several different stacked catalyst bed reactor systems (CS1, CS2, CS3) and for a single catalyst bed reactor system (CS4).
    [018] Figure 6 shows the hydrodesulfurization activity (HDS), that is, the temperature required in relation to the base temperature of the catalyst to achieve a sulfur concentration of 10 ppmp in the diesel product, in the processing of a running diesel in straight high end line to produce an ultra low sulfur diesel product as a function of time in operation (TOS) for the inventive Co/Mo catalyst composition and for the comparative Co/Mo catalyst composition. The test results shown are for the three different test condition sets (Condition Set 1, Condition Set 2, and Condition Set 3).
    [019] Figure 7 shows the hydrodenitrogenation (HDN) activity, that is, the temperature required in relation to the temperature of the base catalyst to achieve a nitrogen content of 5 ppmp in the diesel product, in the processing of a racing soleo gas straight-line high end to produce an ultra-low sulfur diesel product as a function of time of operation (TOS) for the inventive composition of the Co/Mo catalyst and for the comparative composition of the Co/Mo catalyst. The test results shown are for the three different test condition sets (Condition Set 1, Condition Set 2, and Condition Set 3).
    [020] The composition of the invention is one that is particularly useful in the catalytic hydro-processing of petroleum or other hydrocarbon feedstocks, or the composition of the invention is one that is convertible by treatment with hydrogen or a sulfur compound or both , in a catalytic composition which has particularly good catalytic properties in the hydroprocessing of hydrocarbon feedstocks.
    [021] It is a significant feature of the inventive composition that, by using a heterocyclic compound selected from a specifically defined group of polar heterocyclic compounds, as more fully described elsewhere in this document, to impregnate its support material which includes, among other components, a catalytic metal, a composition is provided having certain catalytic properties which are enhanced over alternative catalyst compositions. The inventive composition has been found to have enhanced catalytic properties over those of certain catalyst compositions prepared by using a mixture of a polar additive and hydrocarbon oil.
    [022] Another beneficial attribute of the invention is that the composition does not need to be calcined or have sulfur added to it prior to placing it in a reactor vessel or within a reactor system for use in either the hydrodesulfurization or hydrodenitrogenation of a feedstock of hydrocarbon. This feature provides the particular benefit of significantly reducing certain costs that are associated with the manufacture and treatment of the composition, and allows the use of in situ activation methods that produce a catalytic composition that exhibits significantly improved hydrodesulfurization or hydrodenitrogenation, or both have catalytic activity over certain other compositions of the hydrotreating catalyst.
    [023] The composition of the invention still allows an improved procedure in the beginning of the hydrotreatment reactor systems.
    [024] The composition of the invention includes a support material that has incorporated therein or is loaded with a metal component, which is or can be converted to a metal compound that has activity towards the catalytic hydrogenation of sulfur compounds organic or organic nitrogen. As such, it has application in the hydrotreating of hydrocarbon raw materials.
    [025] The support material containing the metallic component further has incorporated therein a heterocyclic compound as an additive to thereby provide an additive-impregnated composition of the invention.
    [026] The support material of the inventive composition can comprise any suitable inorganic oxide material that is typically used to transport catalytically active metal components. Examples of useful possible inorganic oxide materials include alumina, silica, silica-alumina, magnesia, zirconia, boria, titania and mixtures of any two or more of such inorganic oxides. Preferred inorganic oxides for use in forming the support material are alumina, silica, silica-alumina and mixtures thereof. But preferred, however, is alumina.
    [027] In preparing various embodiments of the inventive composition, the metallic component of the composition may be incorporated into the support material by any suitable method or means providing loading or incorporation into the support material of an active metal precursor. Thus, the composition includes the support material and a metal component.
    [028] A method of incorporating the metallic component into the support material includes, for example, co-weighting the support material with the active metal or metal precursor to produce a co-weighted mixture of the two components. Or, another method includes co-precipitating the support material and metal component to form a co-precipitated mixture of the support material and metal component. Or, in a preferred method, the support material is impregnated with the metallic component using any of the known impregnation methods, such as incipient moisture, to incorporate the metallic component into the support material.
    [029] When using an impregnation method to incorporate the metallic component into the support material, it is preferred for the support material to be formed into a formed particle comprising an inorganic oxide material and thereafter loaded with a metal precursor active, preferably, by impregnating the formed particle with an aqueous solution of a metal salt to give the metal-containing support material of a metal salt solution.
    [030]To form the molded particle, the inorganic oxide material, which is preferably in powder form, is mixed with water and, if desired or necessary, a peptizing agent and/or a binder to form a moldable mixture in a cluster. It is desirable for the mixture to be in the form of an extrudable paste suitable for extrusion into extruded particles, which can be of various shapes, such as cylinders, trilobes, etc., and nominal sizes, such as 1/16", 1/8" , 3/16", etc. The carrier material of the inventive composition, therefore, preferably is in a molded particle comprising an inorganic oxide material.
    [031] The molded particulate is then dried under standard drying conditions which may include a drying temperature in the range of 50°C to 200°C, preferably from 75°C to 175°C, and more preferably from 90°C to 150°C.
    [032] After drying, the molded particle is calcined under standard calcination conditions which may include a calcination temperature in the range of 250°C to 900°C, preferably 300°C to 800°C, and more preferably from 350 °C to 600 °C.
    [033] The calcined molded particle may have a surface area (determined by the BET method employing N2, ASTM test method D 3037) that is in the range of 50 m2/g to 450 m2/g, preferably 75 m2/g 400 m2/g, and more preferably from 100 m2/g to 350 m2/g.
    [034] The average pore diameter in angstroms (A) of the calcined molded particle is in the range from 50 to 200, preferably from 70 to 150, and more preferably from 75 to 125.
    [035] The pore volume of the calcined molded particle is in the range of 0.5 cm3/g to 1.1 cm3/g, preferably, from 0.6 cm3/g to 1.0 cm3/g, and more preferably, from 0.7 to 0.9 cm 3 /g.
    [036] Less than ten percent (10%) of the total pore volume of the calcined molded particle is contained in pores having a pore diameter greater than 350 A, preferably less than 7.5% of the total pore volume of the Calcined soft particle is contained in pores which have a pore diameter greater than 350 A, and more preferably less than 5%.
    [037]References in this document for the pore size distribution and pore volume of the calcined molded particle are to those properties as determined by mercury intrusion porosimetry, test method of ASTM D 4284. pore size of the calcined soft particle is by 140° with a surface tension of mercury of 474 dyne/cm at 25°C.
    [038] In a preferred embodiment of the invention, the calcined molded particle is then impregnated in one or more impregnation steps with a metal component using one or more aqueous solutions containing at least one metal salt in which the metal compound of the solution of metal salt is an active metal or active metal precursor.
    [039] The metal elements are those selected from Group 6 of the Periodic Table of IUPAC elements (eg chromium (Cr), molybdenum (Mo), and tungsten (W)) and Groups 9 and 10 of the Periodic Table of IUPAC Elements (eg cobalt (Co) and nickel (Ni)). Phosphorus (P) is also a desired metallic component.
    [040]For Group 9 and 10 metals, metal salts include Group 9 or 10 metal acetates, formates, citrates, oxides, hydroxides, carbonates, nitrates, sulfates, and two or more thereof. Preferred metal salts are metal nitrates, for example, such as nickel or cobalt nitrates, or both.
    [041]For Group 6 metals, metal salts include Group 6 metal oxides or sulfides. Salts containing the Group 6 metal and ammonium ion, such as ammonium heptamolybdate and ammonium dimolybdate, are preferred.
    [042] The concentration of metal compounds in the impregnation solution is selected so as to provide the desired metal content in the final composition of the invention taking into account the pore volume of the support material in which the aqueous solution is to be impregnated and the amounts of the additive of the heterocyclic compound that is to be incorporated later in the support material that is loaded with a metal component. Typically, the concentration of metal compound in the impregnation solution is in the range of 0.01 to 100 moles per liter.
    [043] The metal content of the support material that has the metallic component incorporated into it may depend on the application for which the additive impregnated composition of the invention is to be used, but generally for hydroprocessing applications, the metallic component of Group 9 and 10, i.e. cobalt or nickel, may be present in the support material which has a metallic component incorporated therein in an amount in the range of 0.5% by weight to 20% by weight, preferably 1% by weight to 15% by weight, and more preferably from 2% by weight to 12% by weight.
    [044] The Group 6 metallic component, i.e. molybdenum or tungsten, preferably molybdenum, may be present in the support material that has a metallic component incorporated into it in an amount ranging from 5% by weight to 50% by weight , preferably from 8% by weight to 40% by weight, and more preferably from 12% by weight to 30% by weight.
    [045]The weight percentages referenced above for metal components are based on the dry support material and the metal component as the element, regardless of the actual shape of the metal component.
    [046]To provide the additive-impregnated composition of the invention, the additive of the heterocyclic compound is incorporated into the support material that has also incorporated into it, as described above, the active metal precursor. The heterocyclic compound additive is used to fill a significant portion of the available pore volume of the support material pores, which is already loaded with the active metal precursor, to thereby provide a composition that comprises, or consists of, essentially of, or consists of, a support material that contains a metallic component and an additive of the heterocyclic compound.
    [047] The preferred method of impregnating the metal-laden support material can be any standard well-known pore filling methodology, whereby the pore volume is filled taking advantage of capillary action to remove liquid from the pores of the material. metal loaded bracket. It is desirable to fill at least 75% of the pore volume of the metal-laden support material with the additive of the heterocyclic compound. It is preferred for at least 80% of the pore volume of the metal-laden support material to be filled with the heterocyclic compound additive, and more preferred for at least 90% of the pore volume to be filled with the heterocyclic compound additive.
    [048] The composition can be installed, as is, in a reactor vessel or within a reactor system that is about to go through a start-up procedure in preparation, or prior to the introduction of a sulphuration feed that may include a sulphurizing agent or a hydrocarbon feedstock that contains a concentration of an organic sulfur compound.
    [049] It is a significant aspect of the invention that the support material loaded with an active metal precursor is not calcined or sulfurized prior to its loading into a reactor vessel or system for its ultimate use as a hydrotreating catalyst, but which can be sulfurized, in situ, in a delayed feed introduction start-up procedure. The start-up procedure of delayed feed input is described more fully below. Furthermore, it has been determined that an improvement in catalytic activity is obtainable when, prior to the hydrogen treatment and sulphuration, the support material loaded with the active metal precursor is filled with the additive of the heterocyclic compound. In this way, not only are certain economic benefits realized by eliminating, or at least not incurring, the costs associated with calcination and sulfuration of the catalyst before its release and use, but also a more active catalyst is obtained.
    [050] It has been found that the support material loaded with an active metal precursor that is impregnated with the additive of the heterocyclic compound prior to treatment with hydrogen followed by treatment with a sulfur compound prepares a hydrotreating catalyst that has higher hydrodesic activities. - sulfurization and hydrodenitrogenation than the support material, loaded with an active metal precursor, but which has instead been impregnated with a mixture of a polar additive such as dimethylformamide and a hydrocarbon oil prior to the treatments of hydrogen and sulfur.
    [051] In preparing the inventive composition, any suitable method or means may be used to impregnate the metal-loaded support material with the additive of the heterocyclic compound. The preferred method of impregnation can be any standard well-known pore filling methodology, whereby the pore volume is filled taking advantage of the capillary action of drawing liquid from the pores of the metal-laden support material. It is desirable to fill at least 75% of the pore volume of the metal-laden support material with the additive of the heterocyclic compound. It is preferred for at least 80% of the pore volume of the metal-laden support material to be filled with the heterocyclic compound additive, and more preferred for at least 90% of the pore volume to be filled with the heterocyclic compound additive.
    [052] In one embodiment of the invention, it is desirable for the catalytic composition to have an absence of the hydrocarbon oil material. The hydrocarbon oil that is absent from the composition of this embodiment may include hydrocarbons that have a boiling temperature in the range of 100°C to 550°C and more specifically from 150°C to 500°C. Possible hydrocarbon oils to be excluded from the support material may include crude oil distillation fractions such as, for example, heavy naphtha containing boiling hydrocarbons perhaps in the range of 100°C to 210°C, kerosene, diesel and diesel.
    [053] The most specific hydrocarbon oil that should be excluded in the amounts of the composition material in this embodiment are those that include olefin compounds that are liquid at the elevated contact temperature of the hydrogen-containing gaseous atmosphere during treatment therewith. Such olefins are those that have a carbon number greater than 12 and generally have a carbon number in the range of 12 to 40 carbons. More specifically, olefin compounds are those that have 14 to 38 carbons, and more specifically, the carbon number is in the range of 16 to 36 carbons. Olefins can be a mixture with non-olefinic hydrocarbons such as alkanes or aromatic solvents or any of the above referenced petroleum distillation fractions such as heavy naphtha, kerosene, diesel and gas oil.
    [054] In view of the above, an embodiment of the inventive catalyst composition has an absence of material of or an absence of a hydrocarbon oil, but instead the inventive catalyst composition comprises, or consists essentially of, , or consists of, as a support material containing a metal component, either a metal salt solution or an active metal precursor and an additive of the heterocyclic compound. The hydrocarbon oil can be a mixture of hydrocarbons having a boiling temperature in the range of 100°C to 550°C or 150°C to 500°C or any of the hydrocarbon oils containing olefins as described above.
    [055] What is meant in this document by the use of the term "absence of material" is that the amount of hydrocarbons present in the composition is such that it has no material effect upon the ultimate catalytic performance of the final catalytic composition of the invention either before or after of its treatment with hydrogen or sulfur, or both. Thus, an absence of hydrocarbon material from the composition may, however, allow the presence of quantities of non-material from the hydrocarbons that have no effect on catalyst performance.
    [056] In general, the olefin content of the hydrocarbon oil to be excluded in an amount of material must be above 5% by weight, and in certain cases it may exceed 10% by weight, or even exceed 30% by Weight. Olefin compounds can include mono-olefins, or they can include olefins with multiple carbon double bonds.
    [057] The heterocyclic compound that is used as an additive in preparing the inventive composition is any suitable polar, heterocyclic compound that provides the benefits and has the characteristic properties as described in that document. Specifically, the heterocyclic compound additive of the composition is selected from the group of polar, heterocyclic compounds having the formula: CxHnNyOz, wherein: x is an integer of 3 or more; y is either zero or an integer in the range 1 to 3 (ie, 0, 1, 2, or 3); z is either zero or an integer in the range 1 to 3 (ie, 0, 1, 2, or 3); and n is the number of hydrogen atoms required to fill the remaining bonds with the carbon atoms of the molecule.
    [058] Preferred additive compounds are those heterocyclic compounds that contain either nitrogen or oxygen as the member of the heteroatom of their ring, such as molecular compounds that have a lactam structure or a cyclic ester structure or a cyclic ether structure.
    [059]Lactam compounds, or cyclic amides, may include compounds that have such general structures as β-lactam, Y-lactam, and δ-lactam in which the nitrogen atom may, instead of a hydrogen atom, have attached to it an alkyl group having from 1 to 6 or more carbon atoms and any of the carbon atoms, other than the carbonyl portion, present in the ring structure may have attached to them an alkyl group having from 1 to 6 or more carbon atoms.
    [060] Cyclic ether compounds, or oxacycloalkanes, can include cyclic compounds in which one or more of the carbon atoms within the ring structure are replaced with an oxygen atom. The cyclic ether compound may also include within the ring a carbonyl moiety or any one or more of the carbon atoms present in the ring structure may have attached thereto an alkyl group having from 1 to 6 or more carbon atoms, or the ring can include a carbonyl moiety and one or more carbon atoms that have attached thereto an alkyl group that has 1 to 6 or more carbon atoms.
    [061] Cyclic ester compounds may include lactone compounds that adjust the structure shown above, for example, β-propiolactone, Y-butyrolactone, and δ-valerolactone. Cyclic ester compounds can include cyclic esters that have more than one oxygen atom contained within the ring structure.
    [062] The most preferred additive compounds are those heterocyclic compounds in which the heteroatom is oxygen or nitrogen.
    [063] Examples of more preferred compounds include propylene carbonate, for example, a cyclic ester compound, and N-methylpyrrolidone, for example, a cyclic amide compound.
    [064] A particularly important aspect of the invention is for the support material which has a metallic component incorporated therein to be non-calcined and non-sulfurized when impregnated with the additive of the heterocyclic compound. Cost savings in the preparation of the composition are realized, but no calcination or sulphuration steps have to be carried out. But, in addition, it has been found that when the additive impregnated composition is further subjected to a hydrogen treatment and sulfur treatment, the resulting catalyst composition exhibits increased catalytic activity.
    [065] Prior to incorporation of the heterocyclic compound additive into the support material that has the metal component incorporated therein, particularly when the metal component is added to the support material by impregnation using an aqueous solution of a metal salt (material of metal-impregnated support), it is important for such metal-impregnated support material to be dried so as to remove at least a portion of the volatile liquid contained within the pores of the support material so as to provide pore volume that can be filled. with the additive. The metal-impregnated support material, thereby, is dried under drying conditions that include a drying temperature that is less than a calcining temperature.
    [066] A significant feature of the invention is that the drying temperature under which the drying step is conducted does not exceed a calcining temperature. Thus, the drying temperature should not exceed 400°C, and preferably the drying temperature, at which the metal-impregnated support material is dried, does not exceed 300°C, and more preferably, the drying temperature does not exceed 250°C. It is understood that the drying step will generally be conducted at temperatures lower than the temperatures mentioned above, and typically the drying temperature will be conducted at a temperature in the range of 60°C to 150°C.
    [067] The drying of the metal-impregnated support material is preferably controlled in a manner so as to provide the resulting dried metal-impregnated support material having a volatile content that is in a particular range. The volatile content of the metal-impregnated support material must be controlled so as not to exceed 20% by weight of LOI. LOI, or loss on ignition, is defined as the percentage weight loss of the material after its exposure to air at a temperature of 482°C for a period of two hours, which can be represented by the following formula: (sample weight before exposure minus sample weight after exposure) multiplied by 100 and divided by (sample weight before exposure). It is preferred for the LOI of the dried metal impregnated support material to be in the range of 1 wt% to 20 wt%, and more preferred 3 wt% to 15 wt%. The dried metal-impregnated support material is further impregnated with the heterocyclic compound additive as described earlier in that document.
    [068] The additive impregnated composition of the invention can be treated, either ex situ or in situ, with hydrogen and a sulfur compound and, in fact, it is one of the beneficial features of the invention that allows the shipment and release of a composition unsulfurized to a reactor in which it can be activated, in situ, by a hydrogen treatment step followed by a sulfurization step. As noted above, the additive impregnated composition may first undergo a hydrogen treatment which is then followed with a treatment with a sulfur compound.
    [069]Hydrogen treatment includes exposing the additive-impregnated composition to a gaseous atmosphere containing hydrogen at a temperature varying upwards to 250°C. Preferably, the additive-impregnated composition is exposed to hydrogen gas at a hydrogen treatment temperature in the range of 100°C to 225°C, and more preferably, the hydrogen treatment temperature is in the range of 125°C at 200°C.
    [070] The partial pressure of hydrogen in the gaseous atmosphere used in the hydrogen treatment step can generally be in the range of 1 bar to 70 bars, preferably 1.5 bar to 55 bars, and more preferably 2 bar at 35 bars. The additive-impregnated composition is in contact with the gaseous atmosphere at the above-mentioned temperature and pressure conditions for a hydrogen treatment time period in the range of 0.1 hour to 100 hours, and preferably the period of hydrogen treatment time is 1 hour to 50 hours, and more preferably 2 hours to 30 hours.
    [071] Sulfuration of the additive-impregnated composition after it has been treated with hydrogen can be done using any conventional method known to those skilled in the art. Thus, the hydrogen treated additive impregnated composition may be in contact with a sulfur-containing compound, which may be hydrogen sulfide or a compound that is decomposable to hydrogen sulfide, under the contact conditions of the invention.
    [072] Examples of such decomposable compounds include mercaptans, CS2, thiophenes, dimethyl sulfide (DMS), and dimethyl disulfide (DMDS).
    [073] Also, preferably, sulfuration is carried out by contacting the composition treated with hydrogen, under the appropriate conditions of sulfurization treatment, with a hydrocarbon feedstock that contains a concentration of a sulfur compound. The sulfur compound of the hydrocarbon feedstock may be an organic sulfur compound, particularly one that is typically contained in petroleum distillates that are processed by hydrodesulfurization methods.
    [074] Suitable sulfurization treatment conditions are those that prepare the conversion of the active metal components of the hydrogen treated additive impregnated composition to its sulfurized form. Typically, the sulfurization temperature at which the hydrogen-treated additive impregnated composition is in contact with the sulfur compound is in the range of 150°C to 450°C, preferably, from 175°C to 425°C, and more preferably from 200°C to 400°C.
    [075] When using the hydrocarbon feedstock that is to be hydrotreated using the catalytic composition of the invention to sulfur the hydrogen-treated composition, the sulfurization conditions may be the same as the process conditions under which the hydrotreatment is carried out. The sulfuration pressure at which the hydrogen-treated additive impregnated composition is sulfurized can generally be in the range of 1 bar to 70 bars, preferably 1.5 bar to 55 bars, and more preferably 2 bar at 35 bars.
    [076] As noted above, one of the benefits provided by the additive impregnated composition of the invention is that it can be used in a reactor system that is started using a so-called delayed feed introduction procedure. In the delayed feed introduction procedure, the reactor system, which includes a reactor vessel containing the additive-impregnated composition, first goes through a heating step to raise the reactor temperature and the additive-impregnated composition contained therein in the preparation for the introduction of a sulphurizing agent or heated hydrocarbon feedstock for processing. This heating step includes introducing the hydrogen-containing gas into the reactor under the hydrogen treatment conditions mentioned above. After the hydrogen treatment of the additive impregnated composition, it is therefore treated with a sulfur compound in the manner as described above mentioned in this document.
    [077] It has been found that the hydrocarbon oil-containing composition, after undergoing a treatment with hydrogen followed by treatment with a sulfur compound, exhibits a greater catalytic activity for the hydrodesulfurization of a distillation feedstock than a similar one , but non-impregnated compositions.
    [078] It is recognized that the additive impregnated composition of the invention, after its treatment with hydrogen and sulfur, is a highly effective catalyst for use in the hydrotreating of hydrocarbon feedstocks. This catalyst is particularly useful in applications involving the hydrodesulfurization and hydrodenitrogenation of hydrocarbon feedstocks, and especially has been found to be an excellent catalyst for use in the hydrodesulfurization of distillation feedstocks, in particular, diesel to make an ultra-low sulfur distillation product that has a sulfur concentration of less than 15 ppmw, preferably less than 10 ppmw, and more preferably less than 8 ppmw.
    [079] In hydrotreating applications, the additive impregnated composition that is used in a delayed feed introduction procedure or otherwise treated with hydrogen and sulfur, as described above, is in contact under appropriate hydrodesulfurization or hydrodenitrogenation , or both, conditions with a hydrocarbon feedstock that typically has a concentration of sulfur or nitrogen, or both.
    [080] The most typical and preferred hydrocarbon feedstock with the additive impregnated composition is a middle oil distillation cut that has a boiling temperature at atmospheric pressure in the range of 140 °C to 410 °C. These temperatures are close to the initial and boiling temperatures of medium distillate. Examples of refinery streams intended to be included within the meaning of middle distillate include straight running distillate fuels at boiling in the boiling range, such as kerosene, jet fuel, light diesel oil, heating oil, heavy diesel oil, and cracked distillates, such as FCC cycle oil, coke oil and hydrocracked distillates. The preferred raw material of the inventive distillate hydrotreating process is a middle distillate boiling in the diesel boiling range of about 140°C to 400°C.
    [081] The sulfur concentration of the middle distillate feedstock can be a high concentration, for example being in the rising range to about 2 percent by weight of the distillate feedstock based on the weight of the elemental sulfur and the total weight of the distillate raw material including the sulfur compound. Typically, however, the distillate feedstock from the inventive process has a sulfur concentration in the range of 0.01% by weight (100 ppmw) to 1.8% by weight (18,000). However, more typically, the sulfur concentration is in the range of 0.1% by weight (1000 ppmw) to 1.6% by weight (16,000 ppmw), and more typically 0.18% by weight (1800 ppmw) to 1.1% by weight (11,000 ppmw).
    [082] It is understood that references in this document for the sulfur content of the distillate feedstock are to those compounds that are normally found in a distillate feedstock or in the hydrodesulfurized distillate product and are chemical compounds that contains a sulfur atom and would generally include organosulfur compounds.
    [083] Also, when referring in this document to "sulfur content" or "total sulfur" or other similar reference to the amount of sulfur that is contained in a raw material, product or other hydrocarbon stream, what it means is the value for total sulfur as determined by ASTM test method D2622-10 entitled "Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescence Spectrometry". The use of percent by weight (% by weight) values of this specification when referring to sulfur content corresponds to the % by weight values as would be reported in test method ASTM D2622 10.
    [084]The middle distillate feedstock may also have a concentration of nitrogen compounds. When you have a concentration of nitrogen compounds, the nitrogen concentration can be in the range of 15 parts per million by weight (ppmp) to 3500 ppmp. More typically, for middle distillate feedstocks that are expected to be handled by the process, the nitrogen concentration of the middle distillate feedstock is in the range of 20 ppmp to 1500 ppmp, and more typically 50 ppmp at 1000 ppmpp.
    [085] When referring in this document to the nitrogen content of a raw material, product or other hydrocarbon stream, the concentration shown is the nitrogen content value as determined by test method ASTM D5762-12 entitled "Standard Test Method for Nitrogen in Petroleum and Petroleum Products by Boat-Inlet Chemiluminescence”. The units used in this descriptive report, such as ppmp or % by weight, when referring to nitrogen content, are the values that correspond to those as reported in ASTM D5762, that is, in micrograms/gram (μg/g) of nitrogen, but converted to the referenced unit.
    [086] The additive impregnated composition of the invention can be employed as a part of any suitable reactor system that prepares the contact of it or its derivatives with the raw material of the distillate under suitable hydrodesulfurization conditions which may include the presence of hydrogen and an elevated total pressure and temperature. Suitable such reaction systems can include fixed catalyst bed systems, boiling catalyst bed systems, slurry catalyst systems, and fluidized catalyst bed systems.
    [087] The preferred reactor system is one that includes a fixed bed of the inventive catalyst contained within a reactor vessel equipped with a feed inlet means, such as a feed nozzle, for introducing the material. from the distillate in the reactor vessel and a reactor effluent outlet means, such as an effluent outlet nozzle, for withdrawing the reactor effluent or the treated hydrocarbon product or the ultra-low sulfur distillate product from the vessel. reactor.
    [088] The hydrotreating process (whether hydrodenitrogenation or hydrodesulfurization, or both) generally operates at a hydrotreating reaction pressure in the range of 689.5 kPa (100 psig) to 13,789 kPa (2000 psig), preferably from 1896 kPa (275 psig) to 10,342 kPa (1500 psig), and more preferably from 2068.5 kPa (300 psig) to 8619 kPa (1250 psig).
    [089] The hydrotreating reaction temperature is generally in the range from 200°C (392°F) to 420°C (788°F), preferably from 260°C (500°F) to 400°C (752°C F), and more preferably from 320°C (608°F) to 380°C (716°F).
    [090] It is recognized that one of the unexpected features of using the inventive additive impregnated composition of the invention is that, in a delayed feed introduction application, the resulting catalyst has a significantly higher catalytic activity than some other alternative catalyst compositions, and thus will generally provide comparatively lower required process temperatures for a given amount of desulfurization or denitrogenation.
    [091] The flow rate at which distillate feedstock is carried to the reaction zone of the inventive process is generally such as to provide a net hourly space velocity (LHSV) in the range of 0.01 h-1 to 10 am-1. The term "liquid hourly space speed", as used in this document, means the numerical proportion of the rate at which the distillate raw material is loaded into the reaction zone of the inventive process in volume per hour divided by the volume of catalyst contained in the reaction zone into which the distillate raw material is carried. The preferred LHSV is in the range from 0.05 h-1 to 5 h-1, more preferably from 0.1 h-1 to 3 h-1 and most preferably from 0.2 h-1 to 2 h -1.
    [092]It is preferred to carry hydrogen along with the distillate feedstock to the reaction zone of the inventive process. In this case, hydrogen is sometimes referred to as the hydrogen treatment gas. The hydrogen treatment gas rate is the amount of hydrogen relative to the amount of distillate feedstock loaded into the reaction zone and is generally in the range up to 1781 m3/m3 (10,000 SCF/bbl). It is preferred for the treatment gas rate to be in the range of 89 m3/m3 (500 SCF/bbl) to 1781 m3/m3 (10,000 SCF/bbl), more preferably 178 m3/m3 (1,000 SCF/bbl) to 1602 m3/m3 (9,000 SCF/bbl), and more preferably from 356 m3/m3 (2,000 SCF/bbl) to 1425 m3/m3 (8,000 SCF/bbl).
    [093] The desulfurized distillate product produced from the process of the invention has a low or reduced sulfur concentration in relation to the raw material of the distillate. A particularly advantageous aspect of the inventive process is that it is capable of providing a deeply desulfurized diesel product or an ultra low sulfur diesel product. As already noted in that document, the low sulfur distillate product may have a sulfur concentration that is less than 50 ppmp or any of the other observed sulfur concentrations as described elsewhere in this document (eg, less than 15 ppmp, or less than 10 ppmpp, or less than 8 ppmpp).
    [094] If the hydrotreated distillate product produced from the process of the invention has a reduced nitrogen concentration relative to the distillate feedstock, it is typically at a concentration that is less than 50 ppmp, and preferably the concentration of nitrogen is less than 20 ppmp or even less than 15 or 10 ppmp.
    [095] The following examples are presented to further illustrate certain aspects of the invention, but they should not be construed as limiting the scope of the invention. Example 1 (Description of Catalyst Compositions Containing Cobalt/Molybdenum)
    [096] This Example 1 presents details regarding the inventive composition of the cobalt/molybdenum catalyst (Catalyst A) and the comparison composition of the cobalt/molybdenum catalyst (Catalyst B) and methods used to prepare these compositions.
    [097] A commercially available alumina carrier was used in preparing the catalyst compositions of this Example I. Table 1 below shows the physical properties of the alumina carrier that was used in the preparations. Table 1 - Typical Alumina Conveyor Properties

    [098] The metal components of the catalyst were incorporated into the carrier by the incipient moisture impregnation technique to produce the following metal composition (oxide base): 14.8% Mo, 4.2% Co , 2.4% P. The impregnation solution included 13.13 parts by weight of phosphoric acid (27.3% P), 13.58 parts by weight of cobalt carbonate (46.2% Co), and 33.09 part by weight Climax molybdenum trioxide (62.5% Mo). The total volume of the resulting solution in the environment was equal to 98% of the Water Pore Volume of 100 parts by weight of the alumina support to provide a support material incorporated into the metal.
    [099] The impregnated carrier or carrier material incorporated into the metal was then dried at 125°C (257°F) for a period of several hours to give a dry intermediate that has an LOI of 8% by weight and a volume of 0.4 cm 3 /g water pore.
    [0100] The dry intermediate aliquot portions were then each impregnated with a selection of one of the following additives or additive mixtures to fill 95% of the dry intermediate pore volume: 100% Catalyst A that produces carbonate of propylene (Sigma Aldrich), and a mixture of 50% dimethylformamide (DMF) and a Catalyst B that produces C18-30 olefin oil. Example 2 (Catalyst Activities in Ultra-Low Pressure Reaction Conditions)
    [0101] This Example 2 presents the results of the hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activity performance test conducted under very low reaction pressure conditions for Catalyst A and Catalyst B when used in the processing of diesel raw materials straight operating system (SRGO).
    [0102] Pilot plant tests were carried out comparing the HDS and HDN activities of Catalyst A and Catalyst B used at very low pressure (VLP), that is, under reaction conditions of 290 psig (10 barg) or 340 psig ( 12 barg). The process conditions used in these tests are shown in Table 2.
    [0103] The feeds used in the tests were lightweight SRGO (Straight Running Gasoil) materials. The properties of the test feeds are shown in Table 3. Table 2. Very Low Pressure Pilot Plant Test Process Conditions
    Table 3. Very Low Pressure (VLP) Pilot Plant Test Supplies


    [0104]Process conditions and feed properties are representative of typical very low pressure ultra-low sulfur (ULSD) diesel operations. The ULSD HDS results obtained in VLP Test 1 and VLP Test 2 are shown in Figure 1. These lots show the Relative Volume Activity (RVA) of Catalyst A and Catalyst B for ULSD HDS, where the content of product sulfur equals 10 ppmp.
    [0105]The HDN results for VLP Test 1 are shown in Figure 2. These lots show the Relative Volume Activity (RVA) of Catalyst A and Catalyst B for deep HDN, where the nitrogen content of the product is equal to 5 ppmp.
    [0106] In both VLP test runs, Catalyst A provided a 20% improvement in ULSD HDS activity over Catalyst B's ULSD HDS activity.
    [0107] In VLP Test 1, Catalyst A showed a 10% higher HDN activity over the HDN activity of Catalyst B.
    [0108] The improvements in catalyst activity of inventive Catalyst A over Comparison Catalyst B are significant. These improvements allow processing of more difficult raw materials to processing raw materials at higher transfer rates or a combination of both. Furthermore, difficult raw material processing or higher feed transfer rates can be successfully carried out in the most challenging reaction conditions of very low pressure.
    [0109]In VLP Test 2, essentially identical product nitrogen concentrations were achieved with both Catalyst A and Catalyst B. This suggests that an HDN floor is achieved with both catalyst compositions.
    [0110]H2 consumption in VLP Test 1 was substantially the same for both Catalyst A and Catalyst B. It is significant that under the very low pressure conditions of VLP Test. 1.Catalyst A provided substantial ULSD HDS and HDN improvements without an increase in H2 consumption. Example 3 (Description of Catalyst Compositions Containing Nickel/Molybdenum)
    [0111] This Example 3 presents details regarding the inventive composition of the nickel/molybdenum catalyst (Catalyst C) and the comparison composition of the nickel/molybdenum catalyst (Catalyst D) and the methods used to prepare these compositions.
    [0112] The alumina carrier used in preparing the catalyst compositions of this Example 3 is the carrier described in Example 1.
    [0113] The metal components of the catalyst were incorporated into the carrier by the incipient moisture impregnation technique to produce the following metal composition (oxide base): 18.0% Mo, 4.5% Ni, 3, 3% P. Alumina support properties are shown in Table 2. The impregnation solution included 20.68 parts by weight of phosphoric acid (27.3% P), 13.58 parts by weight of nickel carbonate (43.7% Ni), and 46.11 parts by weight of Climax molybdenum trioxide (62.5% Mo). The total volume of the resulting solution in the environment was equal to 98% of the Water Pore Volume of 100 parts by weight of the alumina support to provide a support material incorporated into the metal.
    [0114] The impregnated carrier or carrier material incorporated into the metal was then dried at 125 °C (257 °F) for a period of several hours to give a dry intermediate that has an LOI of 10% by weight and a pore volume of 0.33 cc/g water.
    [0115]The aliquot portions of the dry intermediate were then each impregnated with a selection of one of the following additives or additive blends to fill 95% of the dry intermediate pore volume: 100% Catalyst C for production of N-methylpyrrolidone (Sigma Aldrich), and a mixture of 50% dimethylformamide (DMF) and a C18-30 olefin oil production Catalyst D. Example 4 (Low/Moderate Pressure Conditions with Stacked Bed Catalyst System)
    [0116] This Example 4 presents performance test results of the hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activity of various stacked-bed catalyst systems and a single-bed catalyst system in the processing of a material mixture. straight running diesel press and light cycle oil.
    [0117] The stacked bed catalyst systems that were tested are described below. These stacked bed catalyst systems include combinations of the inventive and comparative cobalt/molybdenum catalyst compositions with the inventive and comparative nickel/molybdenum catalyst compositions. Processing conditions are at low to moderate reaction pressure conditions. HDS activity, HDN activity and the results of relative hydrogen consumption for each of the CS1, CS2, CS3 and CS4 catalyst systems are presented.
    [0118]The catalyst systems tested are shown in Table 4. Details regarding Catalyst A, Catalyst B, Catalyst C, and Catalyst D are presented in Examples 1 and 3 above. Table 4. Testing Single Bed and Stacked Bed Catalyst Systems

    [0119] Each of the CS1, CS2, and CS3 catalyst systems in the test was a stacked bed reactor system that includes two cobalt/molybdenum catalyst catalyst beds with one nickel/molybdenum catalyst medium catalyst bed placed between the upper and lower cobalt/molybdenum catalyst beds. The relative volume ratios of the three catalyst beds of the stacked-bed reactor systems were, respectively, 15, 30, and 55 (15/30/55). Thus, the upper catalyst bed included a bed of cobalt/molybdenum catalyst particles that was 15 volume percent (% by volume) of the total catalyst volume of the stacked bed reactor system, the medium catalyst bed includes a bed of nickel/molybdenum catalyst particles that was 30% by volume of the total catalyst volume of the stacked bed reactor system, and the bottom catalyst bed included a bed of cobalt/molybdenum catalyst that was 55% by vol of the total volume of catalyst in the stacked-bed reactor system.
    [0120]Catalyst System 1 (CS1) was the comparative pile bed reactor system. CS1 comprised, in the order of the upper bed, middle bed and lower bed, Catalyst B/Catalyst D/Catalyst B in the proportions mentioned above.
    [0121] Catalyst 2 System (CS2) comprised the inventive Catalyst A placed in both the upper and lower beds of the stacked bed reactor system and the comparison Catalyst B was placed in the middle bed. Thereby, in effect, the Comparison Catalyst B of both the upper and lower beds of CS1 was replaced with the inventive Catalyst A and the Comparison Catalyst D of CS1 was not loaded.
    [0122] Catalyst System 3 (CS3), however, used in the inventive cobalt/molybdenum catalyst, Catalyst A, in both the upper and lower beds of the stacked-bed reactor system and the inventive nickel/molybdenum catalyst , Catalyst C, in the middle bed. Thus, in that case, both Comparison Catalyst B and Comparison Catalyst D of CS1 were respectively replaced with the inventive catalysts Catalyst A and Catalyst C.
    [0123] Catalyst System 4 (CS4) was a tonic law catalyst system with the catalyst bed being composed of inventive cobalt/molybdenum Catalyst A.
    [0124] The feed used in testing the stacked bed and single bed catalyst systems described above was a mixture of 80/20 (volumetric basis) of straight running gas oil (SRGO) and a light cycle oil from a catalytic cracking unit fluidized (LCO). The feed properties used in these pilot plant tests are shown in Table 5. Table 5. Test Feed Properties


    [0125]The process conditions used in processing the feed above in this series of tests are representative of typical commercial operating conditions. These process conditions are shown in Table 6. Table 6. Test Process Conditions

    [0126] Stacked bed catalyst systems are typically used to maximize ULSD HDS activity while controlling or managing H2 consumption. Thus, ULSD and Relative H2 Consumption (RHC) data were obtained for the catalyst systems tested. These data are shown in figure 3 and figure 4.
    [0127]From figure 3 and figure 4, it is seen that at a reaction pressure of 520 psig (36 barg), the CS2 system exhibited an ULSD HDS RVA of 110 as compared to the value 100 for the CS1 system. It is also significant that the CS2 system did not use additional H2 consumption. The CS3 ULSD HDS RVA system for this reaction pressure was 125 compared to the value of 100 for the CS1 system. This is a significant improvement in activity, and only resulted in a small 2% increase in H2 consumption.
    [0128] In comparing the single bed CS4 with CS1, when operated at the reaction pressure of 520 psig (36 barg), CS4 exhibited the same ULSD HDS activity as did the CS1 system, but exhibited an advantageous H2 consumption lower of about 4%.
    [0129] When operated at the highest reactor pressure of 750 psig (52 barg), the CS2 and CS3 systems had ULSD HDS RVA values of 115 and 120, respectively, as compared to the 100 value for the CS1. The corresponding relative H2 consumption values were 104 and 105, respectively. At a pressure of 750 psig (52barg), the CS1 system had an ULSD HDS RVA of 100 and an RHC of 100 compared to respective values of 90 and 95 for the single bed CS4 system. The difference in the relative performance of these two systems at the pressure levels of 520 psig (36 barg) and 750 psig (52 barg) is believed to be due to better utilization of Comparative Catalyst D in the CS1 system at the highest pressure level. elevated.
    [0130]The HDN RVA activities observed with the four catalyst systems tested are shown in figure 5. In general, systems containing NiMo, ie CS1, CS2, and CS3, show higher HDN activity than the system containing CoMo, i.e. CS4, at both pressure levels tested. The higher HDN RVA observed with CS2 as compared to the HDN RVA of CS1 indicates that the inventive Catalyst A increases the HDN capacity of the CoMo/NiMo catalyst system. This is consistent with the results observed with direct comparisons of inventive Catalyst A and comparative Catalyst B. The increased HDN activity of the CS2 and CS3 CoMo/NiMo inventive catalyst systems will be more robust and flexible to fuel change. Incorporate Inventive NiMo Catalyst C into a Stacked Bed Catalyst System with Inventive CoMo Catalyst A results in the HDN activity of the highest catalyst system. Example 5 (Upper End Feed processing with Inventive and Comparison Catalysts)
    [0131]This example 5 presents pilot plant test results of the inventive Catalyst A and Comparison Catalyst B performance in the hydrodesulfurization and hydrodenitrogenation of a high-end feedstock that has significant concentrations of sulfur and nitrogen.
    [0132] The pilot plant test discussed in this Example 5 evaluates the performance of inventive Catalyst A and Catalyst B compared when used in very high end processing, ie, a T95 of at least 795 °F (424 °C) , SRGO power. The properties of this feed are shown in Table 7. Table 7. High End SRGO Feed Properties


    [0133]The Process Condition Sets, ie Set 1, Set 2, and Set 3, used for the high EP feed test are shown in Table 8. These correspond to conditions used in typical business operations that process this type high end power supply. The results obtained with Catalyst A and Catalyst B, when processing the feed described in Table 7 under the process conditions described in Table 8, are shown in figure 6 and figure 7.
    [0134]As shown in Figure 6, the inventive Catalyst A has ULSD HDS activity that is 17 to 19°F (9 to 11°C) more active than the Comparative Catalyst B. This is approximately equal to a ULSD HDS RVA of 135 to 140 for Catalyst A as compared to ULSD HDS RVA 100 for Catalyst B.
    [0135] Figure 7 shows an HDN activity advantage of 9 to 13 °F (5 to 7 °C) for Catalyst A. This translates to an HDN RVA of 120 to 125 for Catalyst A as compared to an HDN RVA of 100 for Catalyst B. Catalyst A's improved ULSD HDS performance can in part be attributed to its superior HDN activity. The ULSD HDS and HDN activity stabilities of Catalyst A are equivalent to those of Catalyst B. Table 8. Elevated Feed End Pilot Plant Test Process Conditions

    [0136] The H2 consumption data obtained with the high EO power test that, under start-up conditions and equivalent product sulfur levels, the H2 consumption with Catalyst A was 95 to 100% of that observed with Catalyst B. Equivalent or lower start-up H2 consumption with Catalyst A is due to the large reduction in start-up temperature requirements (17 to 19°F / 9 to 11°C) required to meet the sulfur level target with the catalyst. This results in a start-up operating temperature requirement that is in a temperature region where the aromatics saturation rate is reduced.
    [0137] It will be apparent to a person skilled in the art that many changes and modifications can be made to the invention without departing from the spirit and scope set forth in this document.
    权利要求:
    Claims (11)
    [0001]
    1. Catalytic composition CHARACTERIZED by the fact that it comprises: a support material that is loaded with an active metal precursor or contains a metallic component of a metal salt solution, in which at least 75% of its pore volume is filled with a heterocyclic additive, wherein the heterocyclic additive is a heterocyclic compound containing oxygen as the heteroatom member of its ring providing a cyclic ester structure.
    [0002]
    2. Catalytic composition, according to claim 1, CHARACTERIZED by the fact that said catalytic composition further comprises a material absent from a hydrocarbon oil.
    [0003]
    3. Catalytic composition, according to claim 1 or 2, CHARACTERIZED by the fact that said support material is further treated, thereafter, with a gas comprising hydrogen.
    [0004]
    4. Catalytic composition according to any one of claims 1 to 3, CHARACTERIZED by the fact that said active metal precursor is a metallic compound that includes a metallic component selected from the group consisting of cobalt, nickel, molybdenum, chromium, tungsten and any combination of two or more of these.
    [0005]
    5. Catalytic composition according to claim 4, CHARACTERIZED by the fact that said metallic component is present in said catalytic composition in an amount ranging from 5% by weight to 50% by weight, wherein the percentages by weight are based on the dry support material and the metallic component as the element.
    [0006]
    6. Catalytic composition, according to any one of claims 1 to 5, CHARACTERIZED by the fact that the additive is propylene carbonate.
    [0007]
    7. Catalytic composition according to claim 4, CHARACTERIZED by the fact that said metallic compound includes a Group 9 and Group 10 metallic component selected from the group consisting of cobalt and nickel, and wherein said metallic component of the Group 9 and from Group 10 is present in said composition in an amount in the range of 0.5% by weight to 20% by weight, and wherein said metallic compound further includes a metallic component from Group 6 selected from the group consisting of in molybdenum and tungsten, and wherein said Group 6 metallic component is present in said composition in an amount in the range of 5% by weight to 50% by weight, wherein the percentages by weight are based on the dry support material and in the metallic component as the element.
    [0008]
    8. Method for manufacturing a catalytic composition as defined in claim 1, CHARACTERIZED in that it comprises: incorporating a metal-containing solution into a support material to provide a support material incorporated into the metal; and filling at least 75% of the pore volume of the metal-incorporated support material with a heterocyclic compound additive to thereby provide an additive-impregnated composition; wherein the heterocyclic additive is a heterocyclic compound containing oxygen as the heteroatom member of its ring providing a cyclic ester structure.
    [0009]
    9. Method according to claim 8, CHARACTERIZED by the fact that it further comprises: contacting said additive-impregnated composition under suitable conditions for treating hydrogen with hydrogen to thereby provide a composition treated with hydrogen.
    [0010]
    10. Method according to claim 9, CHARACTERIZED by the fact that before said filling of said heterocyclic compound additive in the support material incorporated into the metal, said support material incorporated into the metal is dried to contain a volatile content in the range of 3 to 20% by weight of LOI.
    [0011]
    11. Process for hydrotreating a hydrocarbon feedstock, CHARACTERIZED by the fact that it comprises: putting in contact, under appropriate hydrotreating process conditions, said hydrocarbon feedstock with the catalytic composition, as defined in any of claims 1 to 7; and produce a treated product.
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    同族专利:
    公开号 | 公开日
    CA2912544C|2021-11-02|
    TW201501792A|2015-01-16|
    BR112015029993A2|2017-07-25|
    CA2912544A1|2014-12-04|
    EP3003554A1|2016-04-13|
    KR102297213B1|2021-09-02|
    CN105228745A|2016-01-06|
    WO2014194033A1|2014-12-04|
    RU2015156054A3|2018-04-25|
    SG10201810745YA|2019-01-30|
    TWI629100B|2018-07-11|
    CN105228745B|2018-08-07|
    KR20160016783A|2016-02-15|
    RU2673891C2|2018-12-03|
    US20140353213A1|2014-12-04|
    SG11201509604QA|2015-12-30|
    RU2015156054A|2017-07-06|
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    US20180057756A1|2016-08-23|2018-03-01|Shell Oil Company|A polar additive-containing hydroprocessing catalyst and method of making and using thereof|
    FR3057472B1|2016-10-17|2018-11-16|IFP Energies Nouvelles|COBALT CATALYST BASED ON A SUPPORT CONTAINING A MIXED OXIDE PHASE CONTAINING COBALT AND / OR NICKEL PREPARED BY USING A HYDROGENOCARBON COMPOUND|
    FR3073753A1|2017-11-22|2019-05-24|IFP Energies Nouvelles|CATALYST BASED ON A FURANIC COMPOUND AND USE THEREOF IN A HYDROTREATING AND / OR HYDROCRACKING PROCESS|
    FR3083140B1|2018-06-27|2020-06-05|IFP Energies Nouvelles|CATALYST BASED ON A C5 OR C6 ACID ESTER AND ITS USE IN A HYDROPROCESSING AND / OR HYDROCRACKING PROCESS|
    FR3083137A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON A BETA-SUBSTITUTED ESTER AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|
    FR3083130A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON AN ALKYL LACTATE AND ITS USE IN A HYDROPROCESSING AND / OR HYDROCRACKING PROCESS|
    FR3083143A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON AMINO DERIVATIVES AND ITS USE IN A HYDROPROCESSING AND / OR HYDROCRACKING PROCESS|
    FR3083133A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON A BETA-OXYGEN ESTER AND ITS USE IN A HYDROPROCESSING AND / OR HYDROCRACKING PROCESS|
    FR3083138A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON ASCORBIC ACID DERIVATIVES AND ITS USE IN A HYDROPROCESSING AND / OR HYDROCRACKING PROCESS|
    FR3087673A1|2018-10-25|2020-05-01|IFP Energies Nouvelles|SUPPORT-BASED COBALT CATALYST COMPRISING A MIXED OXIDE PHASE CONTAINING COBALT AND / OR NICKEL PREPARED FROM A DILACTONE COMPOUND|
    FR3105931A1|2020-01-06|2021-07-09|IFP Energies Nouvelles|CATALYST BASED ON 2-HYDROXY-BUTANEDIOIC ACID OR 2-HYDROXY-BUTANEDIOIC ACID ESTERS AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|
    法律状态:
    2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-20| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-02-23| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-08-31| 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 29/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361829689P| true| 2013-05-31|2013-05-31|
    US61/829,689|2013-05-31|
    PCT/US2014/039925|WO2014194033A1|2013-05-31|2014-05-29|A hydroprocessing catalyst composition containing a heterocyclic polar compound, a method of making such a catalyst, and a process of using such catalyst|
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