JP2011502205A - A method for upgrading heavy hydrocarbon streams to jet products. - Google Patents

Abstract

  A method of upgrading a heavy hydrocarbon feedstock, comprising contacting the heavy hydrocarbon feedstock with the catalyst in the presence of hydrogen in a reactor system containing a catalyst as the only catalyst, To form a precipitate or cogel, a solution of at least one promoter metal compound; a solution of at least one group VIB metal compound; and a solution of at least one organic oxygen-containing ligand A process for producing a fuel product, which is prepared by sulfidation of a catalyst precursor obtained by mixing with.

Description

  This application claims the benefit of US Provisional Application No. 11 / 932,751, having a filing date of October 31, 2007, under 35 USC120. This application claims priority and benefit with respect to the aforementioned provisional application, the disclosure of which is incorporated herein by reference.

  The present invention relates to a hydroconversion process in which a hydrocarbon feedstock comprising an aromatic compound is contacted with hydrogen in the presence of a catalyst composition comprising at least one Group VIII metal and at least one Group VIB metal. In particular, the present invention is directed to a method for converting a heavy hydrocarbonaceous feedstock to a jet product using a single catalyst system.

  Heavy hydrocarbon streams such as FCC light circulation oil ("LCO"), medium circulation oil ("MCO") and heavy circulation oil ("HCO") have a relatively low value. Typically, such hydrocarbon streams are upgraded by hydroconversion including hydroprocessing and / or hydrocracking.

  Hydroprocessing catalysts are well known to those skilled in the art. Conventional hydroprocessing catalysts are at least one Group VIII metal component and / or at least one, either as a bulk unsupported catalyst or more generally as a catalyst supported by a refractory oxide support. Contains certain Group VIB metal components. Group VIII metal components are usually based on non-noble metals such as nickel (Ni) and / or cobalt (Co). Group VIB metal components include those based on molybdenum (Mo) and tungsten (W). The most commonly used refractory oxide support materials are inorganic oxides such as silica, alumina and silica alumina. Examples of conventional hydroprocessing catalysts are NiMo / alumina, CoMo / alumina and NiW / silica alumina. In some cases, platinum and / or palladium containing catalysts may be used.

  Hydrotreating catalysts are typically used in the process where the hydrocarbon feed is contacted with hydrogen in order to reduce the content of aromatics, sulfur compounds and / or nitrogen compounds. Usually, hydroprocessing methods whose main purpose is to reduce the aromatic content are called hydrogenation or hydrorefining methods, while methods mainly focusing on reducing sulfur and / or nitrogen content are respectively It is called hydrodesulfurization and hydrodenitrogenation. Traditionally, the term “hydrotreating” is used to describe hydrodesulfurization and hydrodenitrogenation, while the term “hydrorefining” is used to describe aromatic hydrogenation. The present invention follows this traditional terminology. Usually, hydrocracking processes convert raw materials to light products such as naphtha or gas by cracking and dealkylation, and to low volume energy density components by non-selective ring opening. One disadvantage of hydrocracking is that it causes more H2 consumption due to cracking, dealkylation and non-selective ring opening. The present invention avoids these disadvantages while producing jet products that not only meet the requirements of the jet standard but also have a high volumetric energy density.

  The present invention is directed to a method for upgrading a heavy hydrocarbon feedstock with an unsupported catalyst in a fixed bed reactor system. In particular, the method of the present invention is directed to a method for upgrading a heavy hydrocarbon feedstock to a jet product having a high volumetric energy density.

  Marmo discloses in US Pat. No. 4,162,961 a circulating oil that is hydrogenated under conditions such that the product of the hydrogenation process can be fractionated.

  Myers et al., In U.S. Pat. No. 4,619,759, discloses a catalytic hydrotreatment of a mixture comprising residual oil and light circulating oil, performed in a dual catalyst bed, wherein the feedstock is The portion of the catalyst bed that is contacted first contains a catalyst comprising alumina, cobalt, and molybdenum, and after passing through the first portion, the second portion of the catalyst bed through which the feedstock passes is added with molybdenum and nickel. And a catalyst containing alumina.

  Kirker et al. In US Pat. No. 5,219,814, high octane gasoline and low sulfur fractions are obtained by hydrocracking a highly aromatic and substantially dealkylated feed over a catalyst. A medium pressure hydrocracking process, wherein the catalyst preferably comprises superstable Y and Group VIII metals, and Group VI metals, and the amount of Group VIII metal content is Incorporated into the framework aluminum content of the ultrastable Y component at a predetermined rate.

  Kalnes, in US Pat. No. 7,005,057, is a very low sulfur diesel in which hydrocarbonaceous feedstocks are hydrocracked at high temperatures and pressures, resulting in conversion to diesel boiling range hydrocarbons. A catalytic hydrocracking process for the production of fuel is disclosed.

  Barre et al., In US Pat. No. 6,444,865, discloses a catalyst used in a process in which a hydrocarbon feedstock containing an aromatic compound is contacted with the catalyst at an elevated temperature in the presence of hydrogen. The catalyst comprises 0.1 to 15%, 2 to 40% by weight manganese and / or rhenium of a noble metal selected from one or more of platinum, palladium and iridium supported on an acidic support.

  Barre et al. In US Pat. No. 5,868,921 is a hydrocarbon distillate that is hydrotreated in one stage by passing the distillate fraction downward over a layered bed of two hydrotreating catalysts. Disclose fractions.

  Fujikawa et al. In US Pat. No. 6,821,412 is supported by an inorganic oxide containing crystalline alumina containing a prescribed amount of platinum, palladium and having a crystallite diameter of 20 to 40 mm. In addition, a catalyst for hydrogen treatment of gas oil is disclosed. Also disclosed is a method for hydrotreating a gas oil containing an aromatic compound under specified conditions in the presence of the above catalyst.

  Kirker et al., In U.S. Pat. No. 4,968,402, discloses a one-step process for producing high octane gasoline from highly aromatic hydrocarbon feedstocks.

  Brown et al. In US Pat. No. 5,520,799 discloses a method for upgrading distillate feedstock. Hydroprocessing catalysts are usually placed in the reaction zone, which is a fixed bed reactor under reaction conditions, to produce low aromatic diesel and jet fuel.

  Soled et al., In US Pat. No. 6,162,350, discloses a slurry hydroprocessing process for upgrading hydrocarbon feedstocks with a bulk mixed metal catalyst preferentially containing Ni—Mo—W. .

  Haluska et al., In US Pat. No. 6,755,963, upgrade hydrocarbon residue feedstock with bulk mixed metal catalysts containing one or more Group VIII metals and one or more Group VIB metals. Discloses a slurry hydrotreating process.

  Riley et al., In US Pat. No. 6,582,590, upgrades a hydrocarbon feedstock with a bulk mixed metal catalyst comprising one or more Group VIII metals and at least two Group VIB metals. A hydroprocessing method is disclosed.

  Riley et al., In US Pat. No. 7,229,548, uses a bulk mixed metal catalyst containing one or more Group VIII metals and at least two Group VIB metals to make naphtha feeds less than about 10 wppm. A slurry hydrotreating process is disclosed that upgrades to a naphtha product of less than about 15 wppm nitrogen and less than about 15 wppm.

  Riley et al. In US Pat. No. 6,929,738 is a bulk mixed metal catalyst comprising one or more Group VIII metals and at least two Group VIB metals with a high sulfur content (from about 3,000 ppm). A two-stage slurry hydrotreating process is disclosed that hydrodesulfurizes the distillate of (high sulfur).

  Hou et al. In US Pat. No. 6,712,955 and Riley et al. In US Pat. No. 6,783,663 contain one or more Group VIII metals and at least two Group VIB metals. A slurry hydrotreating process is disclosed that upgrades a hydrocarbon feedstock with a bulk mixed metal catalyst.

  Demmin et al., In US Pat. No. 6,620,313, discloses a Ni—Mo—W catalyst for use in a multi-stage process for hydrotreating a raffinate feedstock.

In one embodiment of the present invention, a method for upgrading a heavy hydrocarbon feedstock, wherein the heavy hydrocarbon feedstock is combined with the catalyst in the presence of hydrogen in a reactor system containing a catalyst as the only catalyst. The step of contacting, wherein the catalyst has the general formula:
_{^{A V [(M P) (}} OH) x (L) n y] z (M VIB O 4)
Wherein A is at least one of alkali metal cations, ammonium, organic ammonium and phosphonium cations;
^MP is at least one Group VIII metal;
X is at least one oxygen-containing ligand;
M ^VIB is at least one group VIB metal;
M ^P : M ^VIB has an atomic ratio of 100: 1 to 1: 100]
A process for producing a fuel product is provided.

  In one embodiment of the present invention, a method for upgrading a heavy hydrocarbon feedstock, wherein the heavy carbonization is carried out under conditions of hydrotreating in the presence of hydrogen in a reactor system containing a catalyst as the only catalyst. Contacting a hydrogen feedstock with the catalyst, the catalyst comprising a solution of at least one promoter metal compound; a solution of at least one group VIB metal compound; and at least to form a precipitate or cogel; Provided is the method described above, which is prepared by sulfidation of a catalyst precursor obtained by mixing a solution of one organic oxygen-containing ligand at reaction conditions, thereby producing a fuel product.

  The process according to the invention can achieve improved hydrocarbon productivity by increasing the conversion of lower value hydrocarbon streams to higher quality products in a single reactor system.

  The process of the present invention is preferably carried out with a light circulating oil (LCO) feedstock and a catalyst comprising nickel, molybdenum and tungsten to produce a jet product.

  While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are described in detail herein. However, the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is defined by the appended claims. It should be understood that all modifications, equivalents and alternatives falling within the spirit and scope of the invention are intended to be covered.

Definitions FCC—The term “FCC” refers to fluid catalytic cracker, crack-ing or crack-ed.

  As used herein, the terms “feed” and “feed stream” are interchangeable.

  As used herein, “hydrotreating” refers to hydroaddition, hydrorefining, hydrotreating, hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodehydration, including selective hydroopening. By any method carried out in the presence of hydrogen, including but not limited to aromatics, hydroisomerization, hydrodewaxing, hydrocracking. Depending on the type of hydrotreating and reaction conditions, the hydrotreated product can exhibit improved viscosity, viscosity index, saturation content, low temperature properties, volatility and depolarization, and the like.

  Energy density-refers to the heat of combustion released during the combustion of fuel. The amount of heat released depends on whether the water formed during combustion remains in the vapor phase or condenses into a liquid. When water condenses into the liquid phase, it gives up heat of vaporization in the process. In this case, the released heat is called total combustion heat. Pure combustion heat is lower than total combustion heat because water remains in the gas phase (steam). Pure combustion heat is an appropriate value for comparing fuels because the engine emits water as steam. Net volume energy density describes the net energy density of the fuel on a volume basis and is often given in Btu per gallon, for example 125,000 Btu per gallon for jet fuel and 130,000 Btu per gallon for diesel fuel .

LHSV—Liquid space velocity, which is the volumetric flow rate of the liquid feed divided by the volume of the catalyst (ie the volume of the liquid feed at 60 ° F. per hour), given by hr ⁻¹ .

  The periodic table cited herein is a table approved by the IUPAC and the National Bureau of Standards, an example being the Periodic Table of Elements by the Chemical Department of the Los Alamos National Laboratory in October 2001.

  The term “Group VIB metal” refers to chromium, molybdenum, tungsten, and combinations thereof in the form of elements, compounds or ions. The term “Group IIB metal” refers to zinc, cadmium, mercury and combinations thereof in the form of elements, compounds or ions. The term “Group IIA metal” refers to beryllium, magnesium, calcium, strontium, barium, radium and combinations thereof in the form of elements, compounds or ions.

  The term “Group IVA metal” refers to germanium, tin, lead and combinations thereof in the form of elements, compounds or ions. The term “Group VIII metal” refers to iron, cobalt, nickel, ruthenium, rhenium, palladium, osmium, iridium, platinum and combinations thereof in the form of elements, compounds or ions.

  As used herein, the term MP, or “promoter metal”, refers to at least one Group VIII metal; at least one Group IIB metal; at least one Group IIA metal; at least one Group IVA metal; A combination of Group IIB metals; a combination of different Group IIA metals; a combination of different Group IVA, IIA, IIB or VIII metals; a combination of at least Group IIB metals and at least Group IVA metals; a combination of at least Group IIB metals and at least Group VIII metals; A combination of at least a Group IVA metal and at least a Group VIII metal; a combination of at least one Group IIB metal, at least one Group IVA metal and at least one Group VIII metal; and each metal is a Group VIII, IIB At least 2 from any of the Group II, Group IIA and Group IVA metals Metal combination, refers to any of the.

  As used herein, the phrase “one or more” or “at least one” refers to several elements, such as X, Y and Z, or X1-Xn, Y1-Yn and Z1-Zn, or When used to prefix an element type, a single element selected from X or Y or Z or a combination of elements selected from the same common type (such as X1 and X2) and (X1, Y2 And a combination of elements selected from different types (such as Zn).

  As used herein, “hydroconversion” or “hydrotreatment” refers to methanation, water gas shift reaction, hydrogenation, hydrotreatment, hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodearomatization. Means any process performed in the presence of hydrogen, including, but not limited to, hydrocracking processes including group, hydroisomerization, hydrodewaxing and selective hydrocracking. Depending on the type of hydroprocessing and reaction conditions, the hydroprocessing product can exhibit improved viscosity, viscosity index, saturation content, low temperature properties, volatility and depolarization, and the like.

  As used herein, the term “catalyst precursor” refers to at least one promoter metal (eg, one or more Group VIII metals, one or more Group IIB metals, one or more Group IIA metals). Metal, one or more Group IVA metals and combinations thereof), at least one Group VIB metal; at least one hydroxide; and one or more organic oxygen-containing ligands, It refers to a compound that can become catalytically active as a hydroprocessing catalyst after sulfidation.

  As used herein, the term “neutral charged” refers to the catalyst precursor having no net positive or negative charge. The term “neutral charge catalyst precursor” is sometimes sometimes simply referred to as “catalyst precursor”.

  As used herein, the term “ammonium” refers to organic nitrogen containing a cation such as a cation having the chemical formula NH 4+ or an organic quaternary amine.

  As used herein, the term “phosphonium” refers to a cation having the chemical formula PH4 +, or a cation containing organophosphorus.

  The term oxoanion refers to monomeric oxoanions and polyoxometalates. As used herein, the term “mixture” refers to a physical combination of two or more substances. A “mixture” may be homogeneous or heterogeneous and any physical state or combination of physical states.

  The term “reagent” refers to a raw material that can be used to produce the catalyst precursor of the present invention. When used in connection with a metal, the term “metal” means that the reagent is present in the form of a metal compound rather than in metal form.

  As used herein, the term “carboxylate” refers to any compound containing a carboxylate or carboxylic acid group in a deprotonated or protonated state.

  As used herein, the term “ligand” may be used interchangeably with “chelating agent” (or chelator or chelating reagent) and forms a larger complex such as a catalyst precursor group VIB and / or Or refers to an additive that binds to metal ions, such as a promoter metal.

  As used herein, the term “organic” means containing carbon, which may be of biological or non-biological origin.

  As used herein, the term “organic oxygen-containing ligand” refers to any compound comprising at least one carbon atom, at least one oxygen atom and at least one hydrogen atom, wherein the oxygen atom is Having one or more electron pairs available for coordination to the promoter metal (s) or group VIB metal ions. In one embodiment, the oxygen atom is negatively charged at the pH of the reaction. Examples of organic oxygen-containing ligands include, but are not limited to, carboxylic acids, carboxylates, aldehydes, ketones, enolate forms of aldehydes, enolate forms of ketones, hemiacetals and hemiacetal oxoanions.

  The term “cogel” refers to a hydroxide coprecipitate (or precipitate) of at least two metals containing a water-rich phase. “Cogelation” refers to the process of forming a cogel or precipitate.

A. Overview In one embodiment, the present invention provides:
(A) preparing a catalyst by sulfidation of a catalyst precursor comprising at least one promoter metal hydroxide, at least one group VIB metal oxoanion, and a coordinating ligand comprising at least one oxygen. Performing steps; and
(B) A method for upgrading heavy hydrocarbons comprising reacting a heavy hydrocarbon feed stream with a catalyst in the presence of hydrogen in a fixed bed reactor.

B. Feedstocks Heavy hydrocarbon feedstocks can be upgraded to products having a boiling range within the jet boiling range. Hydrocarbon feedstocks include FCC light, medium and heavy circulating oils; jet and diesel fuel fractions; coke products; coal liquefied oils; products from heavy oil pyrolysis processes; Product from hydrocracking; straight cut fractionated from a crude oil unit; or FCC effluent containing a mixture thereof, from about 250 ° F to about 1200 ° F, preferably from about 300 ° F to about It has the majority of the feedstock with a boiling range of 1000 ° F. The term “majority” as used herein and in the appended claims shall mean at least 50% by weight.

  Typically, the feedstock may comprise at least 20% by weight of a ring-containing hydrocarbon compound containing aromatic moieties, naphthene moieties or both, up to 3% by weight sulfur and up to 1% by weight nitrogen. Preferably, the feedstock may contain at least 40% by weight of the ring-containing hydrocarbon compound. More preferably, the feedstock may contain at least 60% by weight of the ring-containing hydrocarbon compound.

C. Catalyst In one embodiment of the present invention, the catalyst used is prepared from a catalyst precursor that can be sulfided, thereby producing an active catalyst that is used to produce the jet fuel product of the present invention. .

  Catalyst Precursor Formula: In one embodiment, the neutral charge catalyst precursor composition has the general formula Av [(MP) (OH) x (L) ny] z (MVIBO4).

  In the formula, A is one or more monovalent cationic species. In one embodiment, A is at least one of an alkali metal cation, ammonium, organic ammonium, and phosphonium cation.

  MP is at least one promoter metal having an oxidation state P of either +2 or +4, depending on the promoter metal used. MP is selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof. In one embodiment where MP is at least one Group VIII metal, MP has an oxidation state P of +2.

  L is one or more oxygen-containing ligands. L has a neutral or negative charge, and n ≦ 0.

  MVIB is at least one group VIB metal having an oxidation state of +6. MP: MVIB has an atomic ratio between 100: 1 and 1: 100. v-2 + P * z-x * z + n * y * z = 0; and 0 ≦ y ≦ −P / n; 0 ≦ x ≦ P; 0 ≦ v ≦ 2; 0 ≦ z. In one embodiment, L is selected from carboxylates, carboxylic acids, aldehydes, ketones, enolate forms of aldehydes, enolate forms of ketones and hemiacetals, and combinations thereof. In one embodiment, A is selected from monovalent cations such as NH4 +, other quaternary ammonium ions, organic phosphonium cations, alkali metal cations, and combinations thereof.

  In one embodiment where both molybdenum and tungsten are used as the Group VIB metal, the molybdenum to tungsten atomic ratio (Mo: W) is in the range of about 10: 1 to 1:10. In another embodiment, the ratio of Mo: W is between about 1: 1 and 1: 5. In embodiments where molybdenum and tungsten are used as Group VIB metals, the neutral charge catalyst precursor is of the formula Av [(MP) (OH) x (L) ny] z (MotWt'O4). In yet another embodiment where molybdenum and tungsten are used as group VIB metals, replacing chromium with some or all of tungsten in a ratio of (Cr + W): Mo ranging from about 10: 1 to 1:10. Can do. In another embodiment, the ratio of (Cr + W): Mo is between 1: 1 and 1: 5. In embodiments where molybdenum, tungsten and chromium are Group VIB metals, the neutral charge catalyst precursor has the formula Av [(MP) (OH) x (L) ny] z (MotWt′Crt ″ O4). is there.

  In one embodiment, the co-catalyst metal MP is at least one of Group VIII metals of MP having oxidation state +2, and the catalyst precursor formula is Av [(MP) (OH) x (L) ny] z. In (MVIBO4), (v-2 + 2z-x * z + n * y * z) = 0.

  In one embodiment, the promoter metal MP is a mixture of two Group VIII metals, such as Ni and Co. In yet another embodiment, MP is a combination of three metals, such as Ni, Co, and Fe.

  In one embodiment where MP is a mixture of two Group IIB metals such as Zn and Cd, the neutral charge catalyst precursor is of the formula Av [(ZnaCda ′) (OH) x (L) y] z. (MVIBO4). In yet another embodiment, MP is a combination of three metals, such as Zn, Cd and Hg, and the neutral charge catalyst precursor has the formula Av [(ZnaCda′Hga ″) (OH) x (L) ny] z (MVIBO4).

  In one embodiment where MP is a mixture of two Group II metals such as Mg and Ca, the neutral charge catalyst precursor is of the formula Av [(Mgb, Cab ′) (OH) x (L) n y] z (MVIBO4). In another embodiment, where MP is a combination of three Group IIA metals such as Mg, Ca and Ba, the neutral charge catalyst precursor has the formula Av [(MgCab′Bab ″) (OH) x ( L) ny] z (MVIBO4).

  Co-catalyst metal component MP: In one embodiment, the co-catalyst metal (MP) compound is in a dissolved state, and the entire amount of the co-catalyst metal compound is dissolved in the liquid to form a homogeneous solution. In another embodiment, the promoter metal is partially present as a solid and partially dissolved in the liquid. In a third embodiment, it is in a completely solid state.

  The promoter metal compound MP is a metal salt or metal selected from nitrate, hydrated nitrate, chloride, hydrated chloride, sulfuric acid, hydrated sulfuric acid, formate, acetate, hypophosphite and mixtures thereof. It may be a mixture of salts.

  In one embodiment, the promoter metal MP is a nickel compound that is at least partially solid, such as nickel carbonate, nickel hydroxide, nickel phosphate, nickel phosphite, nickel formate, nickel sulfide, nickel molybdate. Water insoluble nickel compounds such as nickel tungstate and nickel oxide, nickel molybdenum alloys, nickel alloys such as Raney nickel, or mixtures thereof.

  In one embodiment, the promoter metal MP is selected from Group IIB and VIA metals such as zinc, cadmium, mercury, germanium, tin or lead in elemental, compound or ionic form, and combinations thereof. In yet another embodiment, the promoter metal MP further comprises at least one of Ni, Co, Fe, and combinations thereof in the form of an element, compound or ion.

  In one embodiment, the co-catalyst metal compound is an at least partially solid state zinc compound, such as zinc carbonate, zinc hydroxide, zinc phosphate, zinc phosphite, zinc formate, zinc sulfide, zinc molybdate. Zinc compounds such as zinc tungstate, zinc oxide and the like, zinc compounds that are hardly soluble in water, and zinc molybdenum alloys.

  In one embodiment, the co-catalyst metal is a Group IIA metal compound and is selected from the group of magnesium, calcium, strontium and barium compounds at least partially in the solid state, eg, carbonate, hydroxide, phosphate Water insoluble compounds such as phosphites, sulfides, molybdates, tungstates, oxides or mixtures thereof.

  In one embodiment, the promoter metal compound is a tin compound that is at least partially in a solid state, such as stannic acid, tin phosphate, zinc formate, tin acetate, tin molybdate, tin tungstate, tin oxide. Tin compounds that are not easily soluble in water, such as tin alloys such as tin molybdenum alloys.

Group VIB metal components:
The Group VIB metal (M ^VIB ) compound can be added as a solid, partially dissolved, or dissolved. In one embodiment, the Group VIB metal compound is selected from molybdenum, chromium, tungsten components, and combinations thereof. Examples of such compounds include, but are not limited to: Ie, molybdenum, tungsten or chromium alkali metals, alkaline earths or ammonium metallates (eg tungstic acid, meta-, para-, hexa-, or polytungstate ammonium, ammonium chromate, molybdate, iso-, peroxo -, Di-, tri-, tetra-, hepta, octa-, or ammonium tetradecamolybdate, alkali metal heptamolybdate, alkali metal orthomolybdate, or alkali metal isomolybdate), phosphomolybdenum Ammonium salt of acid, ammonium salt of phosphotunstic acid, ammonium salt of phosphochromic acid, molybdenum (di- and tri) oxide, tungsten (di- and tri) oxide, chromium or chromium oxide, Buden carbide, molybdenum nitride, aluminum molybdate, molybdic acid, chromic acid, tungstic acid, Mo-P heteropoly anion compound, Wo-Si heteropoly anion compound, WP heteropoly anion compound, W-Si heteropoly anion compound , Ni—Mo—W heteropoly anion compound, Co—Mo—W heteropoly anion compound, or mixtures thereof, added in solid, partially dissolved or dissolved state.

Chelating agent (ligand) L:
In one embodiment, the catalyst precursor composition comprises at least one non-toxic organic oxygen-containing ligand having an LD50 value (as a single oral dose to the rat) of greater than 500 mg / Kg. In the second embodiment, the organic oxygen-containing ligand L has an LD50 value of greater than 700 mg / Kg. In a third embodiment, the organic oxygen containing chelator has an LD50 value of greater than 1000 mg / Kg. The term “non-toxic” as used herein means that the ligand has an LD50 value (as a single oral dose to the rat) of greater than 500 mg / Kg. As used herein, the term “at least one organic oxygen-containing ligand” means that in some embodiments, the composition may have more than one organic oxygen-containing ligand. However, some organic oxygen containing ligands may have an LD50 value of less than 500 mg / Kg, while at least one organic oxygen containing ligand has an LD50 value of more than 500 mg / Kg.

  In one embodiment, the oxygen-containing chelating agent L is formic acid, acetic acid, propionic acid, maleic acid, fumaric acid, succinic acid, tartaric acid, citric acid, oxalic acid, glyoxylic acid, aspartic acid, methanesulfonic acid, ethanesulfonic acid, and the like. Selected from the group of non-toxic organic acid addition salts such as aryl sulfonic acids such as alkane sulfonic acids, benzene sulfonic acids and p-toluene sulfonic acids and aryl carboxylic acids such as benzoic acids. In one embodiment, the oxygen-containing chelator L is maleic acid (708 mg / kg LD).

  In another embodiment, the non-toxic chelator L is glycolic acid (having an LD50 of 1950 mg / kg), lactic acid (3543 mg / kg LD50), tartaric acid (7500 mg / kg LD50), malic acid (1600 mg / kg LD50), citric acid (5040 mg / kg LD50), gluconic acid (10380 mg / kg LD50), methoxyacetic acid (3200 mg / kg LD50), ethoxyacetic acid (1292 mg / kg LD50), malonic acid (1310 mg / kg LD50) LD50), succinic acid (500 mg / kg LD50), fumaric acid (10700 mg / kg LD50), and glyoxylic acid (3000 mg / kg LD50). In another embodiment, the non-toxic chelating agent is selected from the group of organosulfur compounds including, but not limited to, mercaptosuccinic acid (800 mg / kg LD50) and thio-diglycolic acid (500 mg / kg LD50). Is done.

  In yet another embodiment, the oxygen-containing ligand L is a compound containing a carboxylate. In one embodiment, the carboxylate compound includes one or more carboxylate functional groups. In yet another embodiment, the carboxylate compound includes formate, acetate, propionate, butyrate, monocarboxylate, and oxalate, including, but not limited to, pentanoate and hexanoate, Dicarboxylic acids include, but are not limited to, malonate, succinate, glutarate, adipate, malate, maleate or combinations thereof. In a fourth embodiment, the carboxylate compound includes maleate.

  The organic oxygen-containing ligand is mixed with a solution or mixture containing a promoter metal, a solution or mixture containing a Group VIB metal, or a precipitate, solution or mixture combination containing a promoter metal and a Group VIB metal. be able to. The organic oxygen-containing ligand may be in a dissolved state in which the entire amount of the organic oxygen-containing ligand is dissolved in a liquid such as water. The organic oxygen-containing ligand may be partially dissolved and partially solid during mixing with the promoter metal (s), group VIB metal (s), or combinations thereof. .

Method for producing a hydrotreating catalyst precursor:
In this preparation method, the composition and structure of the catalyst precursor can be systematically varied by controlling the relative amounts of various reactions and reaction process elements, the type of reagents, and the length and severity. is there.

  The order of addition of reagents used to form the catalyst precursor may vary. For example, the organic oxygen-containing ligand can be combined with a mixture of promoter metal and Group VIB metal prior to precipitation or cogelation. The organic oxygen-containing ligand can be mixed with the solution of the promoter metal and then added to the solution of one or more group VIB metals. The organic oxygen-containing ligand can be mixed with a solution of one or more Group VIB metals and added to the solution of one or more promoter metals.

Formation of precipitate or cogel with group VIB / promoter metal:
In one embodiment of the method, the first stage is a precipitation or cogelation step, wherein the promoter metal component solution and the Group VIB metal component solution are reacted in a mixture to obtain a precipitate or cogel. Precipitation or cogelation is performed at a temperature and pH at which the promoter metal compound and the Group VIB metal compound precipitate or form a cogel. The solution or at least partially in solution organic oxygen-containing ligand is then combined with the precipitate or cogel to form an embodiment of the catalyst precursor.

  In one embodiment, the temperature at which the catalyst precursor is formed is between 50 and -150 ° C. When the temperature, such as 100 ° C. in the case of water, is below the boiling point of the protic liquid, the process is generally performed at atmospheric pressure. Above this temperature, the reaction is generally carried out at high pressure, such as in an autoclave. In one embodiment, the catalyst precursor is formed at a pressure between about 0 and 3000 psig. In a second embodiment, the catalyst precursor is formed at a pressure between about 100 and 1000 psig.

The pH of the mixture can be varied to increase or decrease the rate of precipitation or cogelation, depending on the desired characteristics of the product. In one embodiment, the mixture is kept at its original pH during the reaction step (s). In another embodiment, the pH is maintained in the range between about 0-12. In another embodiment, the pH is maintained in the range between about 4-10. In further embodiments, the pH is maintained in the range between about 7-10. The pH can be changed by adding a base or acid to the reaction mixture, or by adding a compound that decomposes into hydroxide ions or H ⁺ ions that raise or lower the pH, respectively, with increasing temperature. Examples include urea, nitrite, ammonium hydroxide, inorganic acids, organic acids, inorganic bases and organic bases.

In one embodiment, the reaction of the promoter metal component (s) is performed using a water soluble metal salt, such as zinc, molybdenum, tungsten metal salt. This solution may contain other promoter metal component (s), for example cadmium or mercury compounds such as Cd (NO ₃ ) or (CH ₃ CO ₂ ) ₂ Cd, Co (NO ₃ ) ₂ or (CH ₃ CO ₂ ) It may further comprise a Group VIII metal component comprising a cobalt or iron compound such as ₂ Co, and other Group VIB metal component (s) such as chromium.

In one embodiment, the reaction of the promoter metal component (s) is performed using water soluble tin, molybdenum and tungsten metal salts. This solution further contains other Group IVA metal component (s), eg lead compounds such as Pb (NO ₃ ) ₄ or (CH ₃ CO ₂ ) ₂ Pb, and other Group VIB metal compounds such as chromium compounds. Can be included.

  This reaction is carried out using a suitable metal salt, nickel / molybdenum / tungsten, cobalt / molybdenum / tungsten, nickel / molybdenum, nickel / tungsten, cobalt / molybdenum, cobalt / tungsten or nickel / cobalt / molybdenum / tungsten. Resulting in a combination of objects or cogels. The organic oxygen-containing ligand can be added before or after precipitation or cogelation of the Group VIII and / or Group VIB metal components.

  The metal precursor can be added to the reaction mixture in solution, suspension, or a combination thereof. When soluble salts are so added, they dissolve in the reaction mixture and subsequently precipitate or cogel. The solution can optionally be heated under vacuum to achieve precipitation and water evaporation.

  After precipitation or cogelation, the catalyst precursor can be dried to remove water. Drying can be carried out under atmospheric conditions or under an inert atmosphere such as nitrogen or argon, or under vacuum. Drying can be accomplished at a temperature sufficient to remove water, not removal of organic components. Preferably, drying is performed at about 120 ° C. until a constant weight of catalyst precursor is reached.

Characterization of catalyst precursor:
Characterization of neutral charge catalyst precursors is known to those skilled in the art including, but not limited to, powder X-ray diffraction (PXRD), elemental analysis, surface area measurement, average pore size distribution, average pore volume. Can be implemented using technology. Porosity and surface area measurements can be found in B.C. E. T.A. It can be performed using BJH analysis under nitrogen adsorption conditions.

Features of catalyst precursor:
In one embodiment, the catalyst precursor has an average pore volume of 0.05-5 ml / g as measured by nitrogen adsorption. In another embodiment, the average pore volume is 0.1-4 ml / g. In a third embodiment, the average pore volume is 0.1-3 ml / g.

In one embodiment, the catalyst precursor has a surface area of at least 10 m ² / g. In a second embodiment, the catalyst precursor has a surface area of at least 50 m ² / g. In a third embodiment, the catalyst precursor has a surface area of at least 150 m ² / g.

  In one embodiment, the catalyst precursor has an average pore size of 2-50 nanometers as determined by nitrogen adsorption. In a second embodiment, the catalyst precursor has an average pore size of 3 to 30 nanometers as determined by nitrogen adsorption. In a third embodiment, the catalyst precursor has an average pore size of 4-15 nanometers as determined by nitrogen adsorption.

Molding method:
In one embodiment, the catalyst precursor composition can generally be directly formed into various shapes depending on the intended commercial use. These shapes can be produced by any suitable technique such as extrusion, pelletization, beading or spray drying. If the amount of liquid in the bulk catalyst precursor composition is too high to be applied directly to the molding process, solid-liquid separation can be performed prior to molding.

Addition of agents that form pores Catalyst precursors may be mixed with agents that form pores including, but not limited to, steric acid, polyethylene glycol polymers, carbohydrate polymers, methacrylate esters, and cellulose polymers. Can do. For example, the dry catalyst precursor is mixed with a cellulose-containing material such as methylcellulose, hydroxypropylcellulose or other cellulose ether in a ratio of 100: 1 to 10: 1 (wt% catalyst precursor to wt% cellulose). Water is added until a consistency mixture is obtained that can be extruded and extruded. Examples of commercially available cellulosic pore-forming agents can include methocel (available from Dow Chemical Company), avicel (available from FMC Biopolymer), and porocel (available from Porcel). It is not limited to these. The extrudable mixture can be extruded and then optionally dried. In one embodiment, the drying can be performed under an inert atmosphere such as nitrogen, argon, or under vacuum. In another embodiment, the drying can be performed at an elevated temperature between 70 and 200 ° C. In yet another embodiment, the drying is performed at 120 ° C.

Optional ingredients-Diluent:
The term diluent may be used interchangeably with binder.

  In one embodiment, a diluent is optionally included in the method for producing the catalyst. Generally, the diluent material added has less or no catalytic activity than a catalyst prepared from a catalyst precursor composition (without diluent). Therefore, the activity of the catalyst can be reduced by adding a diluent. Thus, in general, the amount of diluent added in the process of the present invention depends on the desired activity of the final catalyst composition. Depending on the envisaged catalyst application, a diluent amount of 0-95% by weight of the total composition may be appropriate.

  The diluent can be added to the promoter metal (s), the mixture containing the promoter metal, the group VIB metal (s) or the mixture containing the metal simultaneously or sequentially. Alternatively, the cocatalyst and the Group VIB metal mixture can be combined together, followed by the addition of a diluent to the combined metal mixture. It is also possible to mix parts of the metal mixture simultaneously or sequentially, followed by the addition of a diluent and finally the remainder of the metal mixture simultaneously or sequentially. Furthermore, it is also possible to mix the solute state metal mixture with the diluent, followed by the addition of the at least partially solid state metal compound. The organic oxygen-containing ligand is present in at least one metal-containing mixture.

  In one embodiment, the diluent is synthesized with a Group VIB metal and / or promoter metal before being synthesized using the bulk catalyst precursor composition and / or before being added during its preparation. . The synthesis of diluents using any of these metals in one embodiment is performed by impregnating these materials with a solid diluent.

  Diluent material includes any material conventionally applied as a diluent or binder for hydroprocessing catalyst precursors. Examples include silica, normal silica alumina, silica alumina such as silica coated alumina and alumina coated silica, alumina such as (pseudo) boehmite, or gibbsite, titania, zirconia, saponite, bentonite, kaolin, sea foam Cationic or anionic clays such as stone or hydrotalcite, or mixtures thereof. In one embodiment, the binder material is selected from silica, aluminum-doped colloidal silica, silica alumina, alumina, titanic, zirconia, or mixtures thereof.

  These diluents can be applied as is or after peptization. It is also possible to apply to any of the diluents a diluent precursor that is converted during the process. Suitable precursors are, for example, alkali metal aluminates (to obtain an alumina diluent), water glass (to obtain a silica diluent), alkali metal aluminates (to obtain a silica alumina diluent) And mixtures of water glasses, sources of 2, 3, and / or tetravalent metals such as mixtures of water soluble salts of magnesium, aluminum and / or silicon (to prepare cationic clays and / or anionic clays) A mixture, chlorohydrol, aluminum sulfate, or a mixture thereof.

Other optional ingredients:
If desired, other materials including other metals can be added in addition to the components described above. These materials include any materials added during the preparation of conventional hydroprocessing catalyst precursors. Suitable examples are phosphorous compounds, boric compounds, additional transition metals, rare earth metals, fillers or mixtures thereof. Suitable phosphorus compounds include ammonium phosphate, phosphoric acid or organophosphorus compounds. The phosphorus compound can be added at any stage of the process. Suitable additional transition metals that can be added in the process step include, for example, rhenium, ruthenium, rhodium, iridium, chromium, vanadium, iron, cobalt, platinum, palladium, and cobalt. In one embodiment, the additional metal is applied in the form of a water insoluble compound. In another embodiment, the additional metal is added in the form of a water soluble compound. Apart from adding these metals during the process, it is also possible to synthesize the final catalyst precursor composition using any material. For example, an impregnation solution containing any of these additional materials can be impregnated with the final catalyst precursor composition.

Sulfiding agent component:
A neutral charge catalyst precursor of the general formula A _V [(M ^VIII ) (OH) _x (L) ⁿ _y ] _z (M ^VIB O ₄ ) can be sulfurized to form an active catalyst. In one embodiment, the sulfiding agent is in the form of a solution and can be decomposed into hydrogen sulfide under general conditions. In one embodiment, the sulfiding agent is present in an amount greater than the stoichiometric amount required to form the sulfiding catalyst from the catalyst precursor. In another embodiment, the amount of sulfiding agent represents a sulfur to group VIB metal molar ratio of at least 3 to 1 to produce a sulfurized catalyst from the catalyst precursor.

In one embodiment, the sulfiding agent is ammonium sulfide, ammonium polysulfide ((NH ₄ ) ₂ S _x ), ammonium thiosulfate ((NH ₄ ) ₂ S ₂ O ₃ ), thiosulfate (Na ₂ S ₂ O ₃ ). , Thiourea CSN ₂ H ₄ , carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), tert-butyl polysulfide (PSTB) and tert-nonyl polysulfide (PSTN) . In another embodiment, the sulfiding agent is selected from alkali and / or alkaline earth metal sulfides, alkali and / or alkaline earth metal hydrogen sulfides, and mixtures thereof. The use of sulfiding agents including alkali and / or alkaline earth metals may require an additional separation process step to remove alkali and / or alkaline earth metals from the spent catalyst.

  In one embodiment, the sulfiding agent is an aqueous ammonium sulfide solution, which can be synthesized from a refinery off-gas of hydrogen sulfide and ammonia. This synthesized ammonium sulfide is readily soluble in water and can be easily stored in an aqueous solution in a tank prior to use. Since the ammonium sulfide solution is more dense than the residual oil, it can be easily separated in the settling tank after the reaction.

  The sulfiding agent may be elemental sulfur mixed with the catalyst precursor during or before extrusion. Elemental sulfur can be coextruded with the catalyst precursor to form an active catalyst in situ during hydroprocessing.

  In one embodiment, the hydrocarbon feedstock is used as a source of sulfur to perform sulfidation of the catalyst precursor. Sulfurization of the catalyst precursor with the hydrocarbon feed can be carried out in one or more hydroprocessing reactors during hydroprocessing.

Sulfurization process:
Sulfurization of the catalyst precursor to form the catalyst can be performed in situ before introducing the catalyst into the hydroprocessing reactor or in the reactor. In one embodiment, the catalyst precursor is contacted with a sulfiding agent at a temperature of 70 ° C. to 500 ° C. for 10 minutes to 5 days and under the pressure of an H ₂ containing gas to convert to an active catalyst. If the sulfiding temperature is below the boiling point of a sulfiding agent (such as 60-70 ° C. in the case of an ammonium sulfide solution), the process is generally performed at atmospheric pressure. Above the boiling point of the sulfiding agent / optional component, the reaction is generally carried out at high pressure, such as in an autoclave.

  In one embodiment, the sulfiding is performed at a temperature ranging from room temperature to 400 ° C. for 1/2 hour to 24 hours. In another embodiment, the sulfidation is from 150 ° C to 300 ° C. In yet another embodiment, the sulfidation is between 300-400 ° C. under pressure. In a fourth embodiment, the sulfurization is at least one sulfur selected from the group of thiodazole, thioacid, thioamide, thiocyanate, thioester, thiophenol, thiosemicarbazide, thiourea, mercaptoalcohol, and mixtures thereof. An aqueous ammonium sulfide solution is used at a temperature between 0 and 50 ° C. in the presence of additives.

  In one embodiment of the present invention, the catalyst of the present invention can optionally include additional structural support materials such as refractory metal oxide materials such as silica, alumina, magnesia, titania, and the like, and mixtures thereof. The structural support may be in any form including, for example, a monolith, sphere, or hollow cylinder. More specifically, the metal oxide material includes alumina, silica, silica alumina, silicate, aluminosilicate, magnesia, zeolite, activated carbon, titanium oxide, thorium oxide, clay, and any combination of these supports. The “support” may be included. In one embodiment of the invention, preferably the catalyst of the invention can contain between 50% and 95% by weight of a structural support. In one embodiment of the present invention, the preferred support was zirconia.

D. Process Conditions and Equipment In one embodiment, a heavy hydrocarbon feed stream is reacted with a catalyst in the presence of hydrogen in a fixed bed reactor system. The fixed bed reactor system includes at least one reactor. Furthermore, more than one reactor can be used either in series or in parallel, or both. Each reactor used employs the catalyst described herein. By optimizing the Group VIII and VIB metal components and ratios, these catalysts used in the process of the present invention can be placed in one reactor and the LCO directly into the jet product in one reactor. Can be converted.

  The reaction zone contains a fixed bed catalyst. A heavy hydrocarbon feed stream is fed to the reaction zone, which has a temperature of about 300 ° F. to about 900 ° F., thereby producing a reaction product. In a preferred embodiment, the feed stream is LCO and the reaction product is a jet fuel product.

Usually, hydrocarbon feedstock contact occurs in a reactor where the feedstock contacts the catalyst. This reaction involves pressures ranging from 100 psig to 3000 psig, hydrocarbon feed LHSV (liquid space velocity) ranging from 0.1 to 10 hr ⁻¹ , and hydrogen and hydrocarbons ranging from about 400 to 20,000 SCF / bbl. Happens at a ratio of If higher conversion of the hydrocarbon feed is desired, the process optionally includes a separation stage that recovers at least a portion of the product that may contain unconverted feed. Next, at least a portion of the product stream is optionally recycled to the reactor system. If the catalyst is deactivated by coke deposits or other poisons, the catalytic activity can be rejuvenated by regeneration. Suitable methods for regeneration are known to those skilled in the art.

  By treating the hydrocarbon feed under the above conditions, substantially all sulfur and nitrogen compounds can be removed and the aromatic compounds partially hydrogenated. The end result is an aromatics content of less than 25%, a low sulfur and nitrogen content and providing hydrocarbon products within jet fuel specifications. More specifically, this creative method can reduce the amount of sulfur to less than about 15 wppm, more preferably about 10 wppm, and most preferably less than about 5 wppm. This can also reduce the amount of nitrogen to less than about 10 wppm, more preferably less than about 5 wppm, and most preferably less than about 1 wppm.

E. Product The method used in the present invention upgrades a heavy hydrocarbon feedstock to a jet fuel product. The method used produces a jet fuel product having a net combustion heat of at least greater than 125,000 Btu / gal, preferably a net combustion heat of at least 127,000 Btu / gal, more preferably 128,500 Btu / gal, It has been found that it is preferably greater than 129,500 Btu / gal. Furthermore, the product meets jet fuel specifications. In particular, the product has a freezing point of jet fuel of less than −40 ° C. The product has a smoke point greater than 18 mm. The product has a viscosity of -20 degrees Celsius and less than 8 cSt. The product has a density of less than 0.840 g / cc at -20 degrees Celsius.

  Other embodiments will be apparent to those skilled in the art.

  The following examples are presented to illustrate specific embodiments of the invention and should not be construed as limiting the scope of the invention in any way.

(Example 1. Formation of catalyst precursor)
Catalyst precursor of formula (NH ₄ ) ⁺ {[Ni _2.6 (OH) _2.08 (C ₄ H ₂ O ₄ ²⁻ ) _0.06 ] (Mo _0.35 W _0.65 O ₄ ) ₂ } Was prepared as follows. 52.96 g ammonium heptamolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O was dissolved in 2.4 L of deionized (DI) water at room temperature. The resulting solution pH was in the range of 5-6. Then 73.98 g ammonium metatungstate powder was added to the above solution and stirred at room temperature until completely dissolved. 90 ml of concentrated (NH ₄ ) OH was added to this solution with constant stirring. The resulting molybdate / tungstate solution was stirred for 10 minutes and the pH was monitored. This solution had a pH in the range of 9-10. A second solution containing 174.65 g Ni (NO ₃ ) ₂ · 6H ₂ O dissolved in 150 ml deionized water is prepared and heated to 90 ° C., thereby creating a hot nickel solution, then Slowly added to the molybdate / tungstate solution over 1 hour. The resulting mixture was heated to 91 ° C. and stirred for an additional 30 minutes. The pH of the solution was in the range of 5-6. A blue-green precipitate formed and the precipitate was collected by filtration. The precipitate was dispersed in a solution of 10.54 g maleic acid dissolved in 1.8 L DI water and heated to 70 ° C. The resulting slurry was stirred at 70 ° C. for 30 minutes, filtered to produce a precipitate, collected and vacuum dried at room temperature overnight. The material was then further dried at 120 ° C. for 12 hours. The resulting material has a typical XRD pattern with a broad peak at 2.5 mm, indicating that the material contains amorphous Ni-OH. As measured by the BET method, the measured surface area was in the range of 50 to 150 m ² / g, the average pore volume was 0.1 to 0.2 cc / g, and the average pore size was 5 to 50 nm.

(Example 2. Sulfurization)
The 6.5 cc catalyst precursor of Example 1 was placed in a tubular reactor and first purged overnight at 100 ° F. with 700 cc / min N ₂ . The temperature was then raised to 450 ° F. in 4 hours. The N ₂ flow was held at 450 ° F. for 1 hour, then switched to 700 cc / min H ₂ and the pressure increased to 800 psig. The reactor was held at 800 psig for 1 hour at 450 ° F. and 700 cc / min H ₂ . Next, 36 cc / hr of a sulfurized raw material containing 6% by weight of DMDS (dimethyl disulfide) in n-heptane was introduced into 800 psig, 700 cc / min of H ₂ at 450 ° F., and kept under these conditions for 2 hours. did. Subsequently, the temperature was increased from 450 ° F. to 650 ° F. in 4 hours and held at 650 ° F. for 2 hours. The temperature was dropped from 650 ° F. to about 300 ° F. as soon as possible while still keeping the sulfide raw material. The sulfurization feed was then stopped and the pressure was raised to a preselected reaction pressure such as 1000 psig and the H ₂ flow rate was adjusted to 77.2 cc / min. At this stage, began FCCLCO flow rate of 6.5cc / hr, 1000psig, _{H 2} flow rate of 77.2cc / min, at about 300 ° F. Subsequently, the reactor temperature was raised to a preselected reaction temperature, such as about 300 ° F. to 600 ° F., at a rate of 1 ° F / min. The reaction was then allowed to proceed at 6.5 cc / hr feedstock, 77.2 cc / min H ₂ , 600 ° F. and 1000 psig.

(Example 3. Catalyst)
The following catalysts were used in the examples or comparative examples of the present invention.

  (1) The catalyst of the present invention is hereinafter referred to as Ni-Mo-W and was prepared according to Examples 1 and 2.

  (2) The hydrotreating catalyst containing molybdenum and nickel supported on an alumina base is hereinafter referred to as Ni-Mo.

  (3) The hydrorefining catalyst containing platinum and palladium supported on a mixed silica alumina / alumina substrate is hereinafter referred to as Pt-Pd.

(Example 4. Feedstock)
Table 1 discloses the properties of the feedstock used in the present invention. The feedstock is light recycled petroleum (LCO) product from a refinery fluid catalytic cracking unit. The feedstock was also analyzed by simulated distillation. The results of the simulated distillation are listed in Table 2. This feedstock is not hydrotreated.

(Example 5)
Upgrade of LCO to jet fuel using Ni-Mo-W catalyst of the present invention as a single catalyst in a single fixed bed reactor The FCCLCO feed described in Table 1 and Table 2 of Example 4 is Hydrotreatment was carried out in a single fixed bed reactor at a flow rate of 6.5 cc / hr over the described 6.5 cc Ni-Mo-W catalyst of the present invention. The reactor temperature was 600 ° F. and the reactor pressure was 1000 psig. The hydrogen flow rate was 77.2 cc / min.

  The results of the catalytic reaction are also listed in Table 1. The results from simulated distillation are also listed in Table 2. This result indicates that the jet standard is satisfied.

(Comparative Example 1)
Upgrade of LCO to jet fuel using Ni-Mo catalyst as the single catalyst in a single fixed bed reactor For comparison with the inventive Ni-Mo-W catalyst described in Example 5, the table of Example 4 The FCCLCO feed described in 1 and Table 2 was hydrotreated in a fixed bed reactor over 5.9 g Ni-Mo catalyst described in Example 3 at a flow rate of 11.2 cc / hr. In this comparative example, the temperature was 660 ° F. and the pressure was 1700 psig. The hydrogen flow rate was 300 cc / min.

  The results of the catalytic reaction are also listed in Table 1. The results of simulated distillation are also listed in Table 2. As a result, it was found that jet products prepared with such Ni-Mo catalysts did not meet jet specifications, and were described in Example 5, especially due to their high activity at a low pressure of 1000 psig and a low temperature of 600 ° F. The advantage of the Ni-Mo-W catalyst of the present invention is shown.

(Comparative Example 2)
LCO Upgrade to Jet Fuel Using Pt-Pd Hydrorefining in Two Fixed Bed Reactors In Comparative Example 1, the FCCLCO feed described in Table 1 and Table 2 in Example 4 was replaced with 11.2 cc / hr Was hydrotreated in a fixed bed reactor over 5.9 g of Ni-Mo catalyst as described in Example 3. The resulting hydroprocessed product produced in this first reactor was then passed over the 4.7 g platinum / palladium hydrorefining catalyst described in Example 3 at a flow rate of 4 cc / hr. Hydropurified in a fixed bed reactor. The temperature of this second reactor containing the Pt / Pd catalyst was 550 ° F. and the pressure was 1000 psig. The hydrogen flow rate was 100 cc / min. In this way, the jet product is produced by a two-stage hydroprocessing-hydropurification reactor system where each stage contains one catalyst.

  Properties of jet products produced from this two-stage reactor system containing two catalysts are also listed in Table 1. The reaction product was also analyzed by simulated distillation. The results of simulated distillation are also listed in Table 2.

As a result, using such a two-stage hydrotreating that mixes Ni-Mo and Pt / Pd catalyst, for example, has a high net combustion heat of 128,781 Btu / gallon and can be seen with an improved smoke point. Thus, it can be seen that the jet fuel characteristics are improved. Compared to Example 5, which uses only a single Ni-Mo-W catalyst in a single reactor, the method of Comparative Example 2 is undesirable. This is because the hydroprocessing catalyst is used in one reactor and the hydrotreating catalyst is used in another reactor to produce a high energy density jet fuel product. It may be economically disadvantageous to use more than one catalyst and more than one reactor to upgrade the LCO to a high energy density jet fuel product.

Claims (25)

A method for upgrading a heavy hydrocarbon feedstock, comprising:
Contacting the heavy hydrocarbon feedstock with the catalyst in the presence of hydrogen in a reactor system containing the catalyst as the only catalyst, the catalyst having the general formula:
_{^{A V [(M P) (}} OH) x (L) n y] z (M VIB O 4)
Wherein A is at least one of an alkali metal cation, ammonium, organic ammonium and phosphonium cation;
^MP is at least one Group VIII metal;
L is one or more oxygen-containing ligands and has a neutral or negative charge where n ≦ 0;
M ^VIB is at least one group VIB metal;
M ^P : M ^VIB has an atomic ratio of 100: 1 to 1: 100, and 0 ≦ y ≦ −2 / n, 0 ≦ x ≦ 2; 0 ≦ v ≦ 2, and 0 ≦ z. . ]
Wherein said process is used to produce a fuel product.   Light, medium and heavy circulating oils with heavy hydrocarbon feedstock FCC; Jet and diesel fuel cuts; Coke products; Coal liquefied oil; Products from heavy oil pyrolysis process; A process according to claim 1 comprising an FCC effluent comprising a product; straight cut fractionated from a crude oil unit; or a mixture thereof.   The method of claim 1, wherein the fuel product has a net heat of combustion greater than 125,000 Btu / gallon.   The process of claim 1 wherein the catalyst is not supported.   The process of claim 1 wherein the catalyst is supported.   The method of claim 1, wherein the freezing point of the fuel product is less than −40 degrees Celsius.   The method of claim 1, wherein the smoke point of the fuel product is greater than 18 mm.   The method of claim 1, wherein the flash point of the fuel product is greater than 38 degrees Celsius.   The method of claim 1, wherein the density of the fuel product at 20 degrees Celsius is less than or equal to 0.840 g / cc.   The method of claim 1, wherein the viscosity of the fuel product at −20 degrees Celsius is less than 8 cSt.   The method of claim 1, wherein the fuel product is a jet fuel product.   A method for upgrading a heavy hydrocarbon feedstock, wherein the heavy hydrocarbon feedstock is contacted with the catalyst under conditions where hydrotreating is performed in the presence of hydrogen in a reactor system containing a catalyst as the only catalyst. And the catalyst comprises a solution of at least one promoter metal compound; a solution of at least one group VIB metal compound; and at least one organic oxygen-containing coordination to form a precipitate or cogel. Said process, which is prepared by sulfidation of the catalyst precursor obtained by mixing the solution of the child under reaction conditions, thereby producing a fuel product.   Light, medium and heavy circulating oils with heavy hydrocarbon feedstock FCC; Jet and diesel fuel cuts; Coke products; Coal liquefied oil; Products from heavy oil pyrolysis process; 13. The process of claim 12, comprising a product; straight cut fractionated from the crude oil unit; or an FCC effluent containing a mixture thereof.   13. The method of claim 12, wherein the fuel product has a net heat of combustion greater than 125,000 Btu / gallon.   13. A process according to claim 12, wherein the catalyst is not supported.   13. A process according to claim 12, wherein the catalyst is supported.   The method of claim 12, wherein the freezing point of the fuel product is less than −40 degrees Celsius.   The method of claim 12, wherein the fuel product has a smoke point of greater than 8 mm.   The method of claim 12, wherein the flash point of the fuel product is greater than 38 degrees Celsius.   13. The method of claim 12, wherein the density of the fuel product at 20 degrees Celsius is less than or equal to 0.840 g / cc.   The method of claim 12, wherein the fuel product is a jet fuel product.   A product prepared by the method of claim 1.   A product prepared by the method of claim 12.   The process according to claim 1, wherein the feedstock comprises at least 20% by weight of a ring-containing hydrocarbon compound comprising an aromatic moiety, a naphthene moiety or both.   The process of claim 4 wherein the feedstock comprises at least 20% by weight of a ring-containing hydrocarbon compound comprising an aromatic moiety, a naphthene moiety or both.