Use of SSZ-41x zeolite and MTW zeolite for the manufacture of jet fuel and diesel fuel.

Abstract

A process for producing distillate range hydrocarbons using MTW catalyst and / or SSZ-41x catalyst is disclosed.

Description

[Technical Field]

[0001]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 314,505, filed on 28 February 2022, the disclosure of which is incorporated herein by reference.

[0002] The present invention relates to the use of catalysts comprising SSZ-41x and / or MTW for hydrogenating hydrocarbon feedstocks (including hydrocracking and hydroisomerization) for the purpose of producing distillate fuels. [Background technology]

[0002]

[0001] As demand for diesel and jet fuels within their respective boiling point ranges increases globally, interest in raw materials other than crude oil is growing.

[0002] MTW and SSZ-41 have the potential to be substitutes or alternatives to zeolites such as USY, which are commonly used for processing non-renewable petroleum hydrocarbons for liquid fuel production. However, of particular interest is the application of MTW zeolite and SSZ-41 zeolite to the production of fuels derived from renewable sources. Paraffinic hydrocarbons, including n-hexadecane (n-C16) and n-octadecane (n-C18), can be readily produced by hydrodeoxygenation of free fatty acids (e.g., palmitic acid or linoleic acid) present in the form of free acids or triglycerides in renewable vegetable or animal oils. Such paraffins can then be converted to hydrocarbon species with boiling points within the jet range via catalytic hydrocracking (HCR) and / or hydroisomerization (HIS) to create pathways for producing jet fuel from renewable raw materials.

[0003] Selectively converting readily available n-C18 from various renewable raw materials into products with a desired jet boiling point range is challenging. This difficulty hinders attempts to develop economically viable pathways for producing renewable aviation fuel. The use of SSZ-41x zeolite and / or MTW zeolite as key components in HCR / HIS catalysts could provide such a pathway, in addition to their use in conventional HCR / HIS applications. [Overview of the project]

[0004] In one embodiment, a process is provided for producing hydrocarbons within a fractional range, the process comprising contacting a hydrocarbon feedstock with a hydrogenation catalyst under hydrogenation conditions to produce a hydrogenated effluent, and fractionating the hydrogenated effluent to recover one or more hydrocarbon fractions that boil within the range of diesel fuel or jet fuel, wherein the hydrogenation catalyst comprises a carrier component and a metal component supported on the carrier component, the carrier component comprising (i) 0.1% to 75% by weight of MTW zeolite and / or SSZ-41x zeolite in an amount of the total weight of the carrier, (ii) 15% to 85% by weight of amorphous silica-alumina in an amount of the total weight of the carrier, and (iii) 5% to 55% by weight of an alumina binder in an amount of the total weight of the carrier, and the metal component comprises metals of Group 6 and non-precious metals of Groups 8 to 10. In connection with the present invention, the following is further disclosed. [1] A method for producing hydrocarbons within a fractional range, The process involves contacting a hydrocarbon raw material with a hydrogenation catalyst under hydrogenation conditions to produce a hydrogenated effluent, This includes fractionating the hydrogenated effluent and recovering one or more hydrocarbon fractions that boil within the range of diesel fuel or jet fuel, The hydrogenation catalyst comprises a carrier component and a metal component supported on the carrier component, wherein the carrier component comprises (i) 0.1% to 75% by weight of MTW zeolite and / or SSZ-41x zeolite in an amount of the total weight of the carrier, (ii) 15% to 85% by weight of amorphous silica-alumina in an amount of the total weight of the carrier, and (iii) 5% to 55% by weight of an alumina binder in an amount of the total weight of the carrier, and the metal component comprises metals of Group 6 and non-precious metals of Groups 8 to 10, the method. [2] The method according to [1], wherein the hydrocarbon raw material comprises at least 10% by weight of a biological component. [3] The method according to [2], wherein the biological component is obtained from the hydrodeoxygenation of renewable oil. [4] The method according to [1], wherein the hydrocarbon raw material comprises at least 40% by weight of n-paraffin. [5] The hydrogenation treatment conditions are a reaction temperature of 300°C to 500°C, a total pressure of 6 MPa to 30 MPa, a hydrogen supply rate of 800 SL / L to 2000 SL / L, and 0.1 h -1 ~10h -1 The method according to [1], including the liquid space velocity. [6] The aforementioned MTW zeolite contains 25-100 SiO2 2 / Al 2 O 3 The method according to [1], having a molar ratio. [7] The method according to [1], wherein the MTW zeolite is ZSM-12. [8] The aforementioned SSZ-41x zeolite has an SiO2 content of 30 to less than 100. 2 / Al 2 O 3 Molar ratio, and SiO2 between 15 and 75 2 The method according to [1], having a molar ratio of / ZnO. [9] The method according to [1], wherein the MTW zeolite and / or the SSZ-41x zeolite are present in an amount of 0.5% to 25% by weight relative to the total weight of the carrier.

[10] The method according to [1], wherein the amorphous silica-alumina is present in an amount of 50% to 80% by weight relative to the total weight of the carrier.

[11] Before being incorporated into the carrier, the amorphous silica-alumina was 0.5 cm 3 / g~2.0cm 3 Total pore volume per g, average pore diameter of 4 nm to 14 nm, and 400 m 2 / g~550m 2 The method according to [1], having one or more properties of the BET surface area per g.

[12] The method according to [1], wherein the alumina binder is present in an amount of 15% to 35% by weight relative to the total weight of the carrier.

[13] The method according to [1], wherein the Group 6 metal is present in an amount of 5 to 40% by weight in terms of oxides relative to the total weight of the catalyst.

[14] The method according to [1], wherein the metals of groups 8 to 10 are present in an amount of 1 to 10% by weight in terms of oxides relative to the total weight of the catalyst.

[15] The method according to [1], wherein the metal of group 6 is selected from molybdenum and / or tungsten, and the metals of groups 8 to 10 are selected from cobalt and / or nickel.

[16] The method according to [1], wherein the hydrogenation catalyst further comprises an organic dispersant having 2 to 10 carbon atoms and a ratio of the number of carbon atoms to the number of oxygen atoms of 0.6 to 2.

[17] The method according to

[16] , wherein the organic additive is selected from citric acid, gluconic acid, nitrilotriacetic acid, ethylene glycol, or any combination thereof.

[18] The hydrogenation catalyst is P 2 O 5 The method according to [1], further comprising 1 to 10% by weight of phosphorus.

[19] The method according to [1], wherein the hydrogenation catalyst is further sulfurized under sulfurization conditions before contacting the hydrocarbon raw material with the hydrogenation catalyst.

[20] The method according to [1], wherein the diesel fuel or jet fuel is used as a drop-in fuel composition or mixed with an existing fuel composition. [Brief explanation of the drawing]

[0005] [Figure 1] This graph shows the catalytic activity temperature (CAT) versus the hydrogenation rate (HCR) (<500°F) during the hydrogenation of n-octadecane using the MTW catalyst and SSZ-41x catalyst used in Example 1.

[0006] [Figure 2] This graph shows the product fraction yield relative to the HCR conversion rate (<500°F) during the hydrogenation of n-octadecan using the MTW catalyst and SSZ-41x catalyst used in Example 1.

[0007] [Figure 3] This graph shows the freezing point of the jet product fraction against the HCR conversion rate (<500°F) during the hydrogenation of n-octadecan using the MTW catalyst and SSZ-41x catalyst used in Example 1.

[0008] [Figure 4A] This graph shows the cloud point and pour point of the jet product in relation to the HCR conversion rate (<500°F) during the hydrogenation of n-octadecane using the SSZ-41x catalyst used in Example 1.

[0009] [Figure 4B] This graph shows the cloud point and pour point of the jet product in relation to the HCR conversion rate (<500°F) during the hydrogenation of n-octadecan using the MTW catalyst used in Example 1.

[0010] [Figure 5] This graph shows the fraction yield relative to the HCR conversion rate (<700°F) during the hydrogenation of unconverted oil using the MTW catalyst and SSZ-41x catalyst used in Example 2.

[0011] [Figure 6] This graph shows the CAT to HCR conversion rate (<700°F) during the hydrogenation of unconverted oil using the MTW catalyst and SSZ-41x catalyst used in Example 2. [Modes for carrying out the invention]

[0012] definition The boiling point range for jet fuel is specified as 140°C to 300°C. The jet fuel boiling point range is defined as the fraction with an initial boiling point of 140°C or higher, a T10 distillation point of 205°C or lower, and a final boiling point of 300°C or lower. Unless otherwise specified, the distillation point and boiling point may be determined according to ASTM D2887.

[0013] The boiling point range for diesel is defined as 140°C to 375°C. The fractions within the diesel boiling point range are defined as fractions having a T10 distillation point of 140°C or higher, a final boiling point of 300°C or higher, and a T90 distillation point of 375°C or lower.

[0014] The boiling point range for distillate fuels (both jet and diesel) is specified as approximately 140°C to 427°C.

[0015] The "T10" boiling point of the feedstock refers to the temperature at which 10% by weight of the feedstock evaporates. Similarly, the "T90" boiling point refers to the temperature at which 90% by weight of the feedstock evaporates. Appropriate ASTM methods, such as ASTM D86 or ASTM D2887, can be used to measure the boiling point (including fractional boiling point).

[0016] The term "hydrogenation" refers to the process of converting hydrocarbons into more valuable products in the presence of a hydrogenation catalyst and hydrogen.

[0017] The terms “hydrocracking” (“HCR”) and “hydrogenation” refer to any process in which a feed stream of hydrocarbons is brought into contact with a catalyst and hydrogen under high pressure and high temperature to convert at least a portion of the hydrocarbon feed stream into lower boiling point products, thereby resulting in a stream of products with a lower mean boiling point overall, on a weight percentage basis. Hydrocracking is a part of a hydrogenation process. Naturally, “hydrocracking” or “hydrogenation” may also include the hydrogenation isomerization (“HIS”) of long-chain paraffins present in the hydrocarbon stream. Hydrogenation can improve low-temperature flow properties by increasing the proportion of branched paraffins.

[0018] The term "MTW" includes all molecular sieves and their isotypes designated as skeletal MTW by the Structure Commission of the International Zeolite Association. MTW skeletal molecular sieves have a unique pore system consisting of one-dimensional channels containing 12-membered T atomic rings. Examples of MTW skeletal molecular sieves include CZH-5, NU-13, Theta-3, TPZ-12, and ZSM-12.

[0019] The term "SSZ-41x" refers to a zincoaluminosilicate molecular sieve having the skeletal structure of SSZ-41, characterized by (a) an SiO2 / Al2O3 molar ratio of 30 to less than 100 (e.g., 50 to 90 or 60 to 80), (b) an SiO2 / ZnO molar ratio of 15 to 75 (e.g., 20 to 40), and (c) an average crystal size of less than 500 nm (e.g., 50 to 500 nm, or 50 to 250 nm, or 75 to 500 nm, or 75 to 250 nm). SSZ-41 has an average crystal size of at least 1000 nm, as conventionally synthesized according to the teachings of U.S. Patent No. 5,591,421. SSZ-41 has a structure similar to VPI-8 (VET framework type) (a material with a unique one-dimensional channel containing a 12-membered T atomic ring), but differs from VPI-8 in that SSZ-41 has a greater argon retention capacity (e.g., up to approximately three times greater) than reported for VPI-8. SSZ-41 may contain aluminum in its framework structure, whereas VPI-8 does not.

[0020] The term "zincoaluminosilicate" refers to synthetic molecular sieves having a skeletal structure constructed of zinc, alumina, and silica (i.e., repeating tetrahedral units of ZnO4, AlO4, and SiO4).

[0021] The term "unconverted oil" and its acronym "UCO" refer to a high paraffin fraction from a hydrogenation cracker containing hydrocarbons with low nitrogen, sulfur, and Ni content, and with an initial boiling point corresponding to the endpoint of hydrocarbons in the atmospheric gas oil (AGO) range. In certain embodiments, the initial boiling point is in the range of 340°C to 370°C (e.g., 340°C, or 360°C, or 370°C), and the endpoint is in the range of approximately 510°C to 560°C (e.g., 540°C, or 550°C, or 560°C). UCO is also known in the industry by other synonyms such as "hydrowax."

[0022] The term "Cn hydrocarbon" or "Cn" (where n is an integer) refers to a hydrocarbon having that number of carbon atoms. The term "Cn+ hydrocarbon" or "Cn+" refers to a hydrocarbon having a number of carbon atoms equal to or greater than that value. The term "Cn- hydrocarbon" or "Cn-" refers to a hydrocarbon having a number of carbon atoms equal to or less than that value.

[0023] The terms "weight %", "volume %", and "mol %" refer to the weight percentage, volume percentage, or mole percentage of the component relative to the total weight, total volume, or total number of moles of the material containing that component, respectively. In a non-restrictive example, 100 grams of material containing 10 grams of a particular component contains 10% by weight of that component.

[0024] The term "SiO2 / Al2O3 molar ratio" is sometimes abbreviated as "SAR".

[0025] Hydrocarbon raw materials A wide range of petroleum and chemical raw materials can be hydrotreated in accordance with this disclosure. Suitable raw materials include light to heavy fractions, including whole crude oil and reduced crude oil, atmospheric oil, circulating oil, vacuum light oil and coker light oil, as well as unrefined fractions, hydrocracking products, hydrotreated oil, slack wax, Fischer-Tropsch wax, raffinates, and mixtures thereof.

[0026] In some embodiments, at least a portion of the supply material may correspond to material derived from a biological component source. In this specification, biological component material refers to hydrocarbon material derived from biological component sources such as plants, animals, fish, and / or algae. Biological component material can be obtained, for example, by the hydrodeoxygenation and optionally isomerization of renewable oils.

[0027] The supplying material comprises at least about 10% by weight (e.g., at least 25% by weight, or at least 40% by weight, or at least 50% by weight, or at least 75% by weight, or at least 90% by weight, or at least about 95% by weight) of the raw materials relative to one or more biological component sources. Additionally or alternatively, the supplying material may be entirely derived from biological component sources, or the supplying material may comprise about 99% by weight or less (e.g., 90% by weight or less, or 75% by weight or less, or 50% by weight or less) of the raw materials relative to the biological component sources.

[0028] One way to define the feedstock is based on the boiling point range of the feedstock. Typical feedstocks include, for example, those with an initial boiling point and / or T5 boiling point of at least about 400°F (204°C) (e.g., at least about 450°F (232°C)). Additionally or alternatively, the endpoint, T95 boiling point and / or T90 boiling point of the feedstock may be below about 850°F (454°C), for example, below 800°F (427°C), or below about 750°F (399°C). It should be noted that feedstocks with lower T5 boiling points may also be suitable. However, the yield resulting from such low-boiling-point feedstocks can be determined relative to the 400°F+ (204°C+) portion of the feedstock.

[0029] In some embodiments, the raw material may have a higher n-paraffin content. The n-paraffin content of the raw material may be at least 40% by weight (e.g., at least 50% by weight, or at least 75% by weight, or at least 90% by weight, or at least 95% by weight).

[0030] Hydrogenation Hydrogenation can be carried out by exposing the raw material to a hydrogenation catalyst under effective hydrogenation conditions.

[0031] The hydrogenation treatment can be carried out in one or more fixed beds, ebullated - beds, slurry beds, moving beds, continuous stirred - tank reactors (CSTRs), or tubular reactors arranged in series and / or in parallel. The fixed - bed reactor can include a plurality of vessels, a single or multiple catalyst beds in each vessel, and various combinations of hydrogenation catalysts in one or more vessels.

[0032] The reaction conditions during the hydrogenation treatment can be selected to effect a desired level of conversion of the feedstock. The conversion of the feedstock can be defined in terms of converting molecules that boil above a threshold temperature to molecules that boil below that threshold. The conversion temperature can be any convenient temperature, such as 260 °C (500 °F) or 371 °C (700 °F). For example, the process conditions can be selected to achieve a conversion rate of at least 10% of the 260 °C + portion of the feedstock. That is, the conditions are selected to convert at least about 10 wt% of the portion of the feedstock that boils above 260 °C to a portion that boils below 260 °C. In some embodiments, the single - pass conversion amount relative to 260 °C can be at least 20% (e.g., at least 30%, or at least 40%, or at least 50%). Additionally or alternatively, the conversion percentage can be about 80% or less (e.g., 70% or less, or 60% or less). An example of a suitable conversion amount can be a conversion percentage of 30% - 80% (e.g., 40% - 70%).

[0033] Process conditions include a reaction temperature in the range of 300 °C - 500 °C (e.g., 300 °C - 450 °C, or 330 °C - 450 °C), a total pressure in the range of 6 MPa - 30 MPa (e.g., 10 MPa - 20 MPa, or 12 MPa - 18 MPa), a hydrogen feed rate in the range of 800 SL / L - 2000 SL / L (e.g., 1000 SL / L - 2000 SL / L, or 1000 SL / L - 1500 SL / L) (standard liters per liter of hydrocarbon feedstock), and 0.1 h -1 ~10 h -1 (e.g., 0.5 h -1 ~5 h -1 、or 0.5 h -1 ~2 h-1 Examples of liquid-space velocities (LHSV) in the range of ) can be given.

[0034] Hydrogenation is carried out in the presence of hydrogen. Therefore, a hydrogen stream is supplied to or injected into the reactor or reaction zone or hydrogenation zone where the hydrogenation catalyst is located. The hydrogen contained in the hydrogen “process gas” may be either pure hydrogen or a hydrogen-containing gas. A hydrogen-containing gas is a gas stream containing a sufficient amount of hydrogen for the intended reaction (which may be multiple), and may contain one or more other gases (e.g., nitrogen and light hydrocarbons such as methane). The process gas stream introduced into the reaction stage may contain at least 50 vol% (e.g., at least 75 vol%) of hydrogen. Optionally, the hydrogen process gas may be substantially free of impurities such as H2S and NH3 (less than 1 vol%), and / or such impurities may be substantially removed from the process gas before use. Hydrogen may be supplied to the hydrogenation reactor and / or reaction zone simultaneously with the feedstock or separately via a separate gas conduit.

[0035] Following the hydrogenation treatment, the hydrogenated effluent can then be passed through a gas-liquid separator to remove the gaseous portion from the effluent. The liquid-phase effluent from the separator can then be fractionated to produce at least a converted fraction containing products within the fraction range and an unconverted fraction containing products with a higher boiling point range, typically obtained from the unconverted portion. For example, a fractional distillation unit can be used to produce at least a diesel fraction and a jet hydrocarbon fraction. The unconverted portion can then be hydrocracked, and optionally the remaining unconverted portion can be recycled for further hydrocracking. Optionally, a common fractional distillation unit or other separator can be used to separate products within the distillate fuel boiling point range from the unconverted portion of the feedstock having a boiling point range above the distillate fuel boiling point range. Fractionation can be carried out using a distillation unit, such as an atmospheric distillation unit.

[0036] In some cases, the hydrogenated product can be defoamed to obtain a distillate fuel with improved low-temperature fluidity characteristics and a boiling point range.

[0037] The hydrocarbon fractions in the diesel and jet ranges obtained here can be used as a drop-in fuel composition or mixed with existing fuel compositions.

[0038] Hydrogenation catalyst The catalyst used in this hydrogenation process comprises a carrier component and a metal component supported on the carrier component. The carrier component comprises (i) 0.1% to 75% by weight of MTW zeolite and / or SSZ-41x zeolite relative to the total weight of the carrier, (ii) 15% to 85% by weight of amorphous silica-alumina relative to the total weight of the carrier, and (iii) 5% to 55% by weight of an alumina binder relative to the total weight of the carrier. The metal component comprises metals of Group 6 and non-precious metals of Groups 8 to 10.

[0039] In some embodiments, MTW zeolite is ZSM-12.

[0040] Preferably, the zeolite has a low SiO2 / Al2O3 molar ratio. For example, the SiO2 / Al2O3 molar ratio of MTW zeolite may be in the range of 25 to 100 (e.g., 25 to 75, or 25 to 50, or 30 to 100, or 30 to 75, or 30 to 50). SSZ-41x may have an SiO2 / Al2O3 molar ratio in the range of 30 to less than 100 (e.g., 50 to 90), and further in the range of 15 to 75 (e.g., 20 to 40). / The zeolite may have a ZnO molar ratio. Means and methods for quantifying the SiO2 / Al2O3 molar ratio and SiO2 / ZnO molar ratio of zeolites are well known in the art and include atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and X-ray fluorescence (XRF) spectroscopy.

[0041] Preferably, the zeolite is hydrogen type or NH4 +It is of the type (that is, at least some of the original cations that bond to the zeolite are each H + Ions or NH4 + (Replaced by ions). The first method involves direct treatment with an acid, such as a mineral acid (HNO3, HCl, etc.). The second method involves direct exchange using an ammonium salt (e.g., NH4NO3) followed by calcination. Zeolites may contain, at most trace amounts, other cations (e.g., Na). + ) may be included (where "trace amount" means 0.05% by weight or less of the total weight of the zeolite).

[0042] The amount of zeolite in the carrier can be in the range of 0.1% to 75% by weight (for example, 0.5% to 25% by weight) relative to the total weight of the carrier.

[0043] Amorphous silica-alumina (ASA) may include porous amorphous silica-alumina such as SIRAL high-pore volume ASA, but high pore volume is not necessary for the catalyst to be effective. ASA may contain 20% to 50% by weight of silica, with the remainder being alumina.

[0044] The ASA powder, before being incorporated into the catalyst, measured by N2 adsorption at 77K, yielded a volume of 0.5 cm³. 3 / g~2.0cm 3 / g (for example, 0.6cm) 3 / g~1.6cm 3 The total pore volume may be ( / g). The average pore diameter of the ASA powder before incorporation into the carrier may be in the range of 4nm to 14nm (e.g., 5 to 13nm) when measured by the BJH method. The total BET surface area of ​​the ASA powder before incorporation is 400m². 2 / g~550m 2 / g (for example, 410m) 2 / g~510m 2 It may be within the range of / g).

[0045] The amount of ASA in the carrier may be in the range of 15% to 85% by weight (e.g., 50% to 80% by weight) relative to the total weight of the carrier.

[0046] Any α-alumina, η-alumina, θ-alumina, or γ-alumina is a suitable alumina binder for the carrier, with γ-alumina being preferred. The amount of alumina in the carrier may be in the range of 5% to 55% by weight (e.g., 15% to 35% by weight) relative to the total weight of the carrier.

[0047] The carrier may include, if applicable, a refractory binder or matrix material other than alumina to facilitate manufacturing and provide strength. Suitable binders may include at least one of inorganic oxides, such as silica, magnesia, zirconia, chromia, titania, boria, tria, and zinc oxide.

[0048] The carrier used may be in the form of molded particles. The molded carrier can be prepared by any suitable method known to those skilled in the art. The particles may be of various shapes, such as cylindrical or multi-lobed, and may have nominal dimensions such as 1 / 16 inch, 1 / 8 inch, or 3 / 16 inch.

[0049] After forming the carrier particles, they can be impregnated with metal salts using an impregnation solution. Impregnation, such as by simple wetting or ion exchange in solution, is a commonly used technique for introducing metals into catalysts containing carriers. Suitable metal salts may include common salts used for aqueous impregnation of carrier particles for catalysts.

[0050] The hydrogenation treatment includes at least one Group 6 metal and at least one Group 8-10 non-precious metal as the hydride metal or catalyst metal.

[0051] Group 6 metals may include chromium, molybdenum, tungsten, or any combination thereof, preferably molybdenum and / or tungsten. The Group 6 metals may be present in oxide form, typically in amounts ranging from 2% to 70% by weight (e.g., 5% to 40% by weight, or 10% to 30% by weight) relative to the total weight of the catalyst.

[0052] Non-precious metals of Groups 8-10 may include iron, cobalt, nickel, or any combination thereof, preferably nickel. Non-precious metals of Groups 8-10 may be present in oxide form, typically in amounts ranging from 1% to 40% (2% to 15% by weight) relative to the total weight of the catalyst.

[0053] In some embodiments, the total metal content (groups 6 and 8-10 metals) may be in the range of 15% to 55% by weight (e.g., 20% to 40% by weight) of the total weight of the catalyst, in the form of oxides. The amount of metal in the catalyst can be measured, for example, by subjecting the catalyst to XRF or ICP analysis.

[0054] The hydrogenation catalyst may further contain an organic dispersant. The organic dispersant may be an organic compound containing 2 to 10 carbon atoms and having a carbon atom-to-oxygen atom ratio of 0.6 to 2. The organic dispersant may also be a chelating agent. Examples of suitable organic dispersants include glycols (e.g., ethylene glycol) and organic acids (e.g., citric acid, gluconic acid). In some cases, the organic dispersant may be a nitrogen-containing organic compound such as nitrilotriacetic acid. Without being bound by any particular theory, it is thought that the organic dispersant can be removed from the catalyst precursor / catalyst during the heating, calcination, and / or sulfidation steps performed after impregnation to form metal oxides and / or metal sulfides. The dispersant is thought to help adjust the metal distribution throughout the catalyst support.

[0055] When a metal is added to the catalyst by impregnation, the amount of organic dispersant in the impregnation solution can be selected based on the amount of metal in the solution. In some embodiments, the molar ratio of the organic additive to the total metal in the solution may be 0.1 to 5.0 (e.g., 0.1 to 2.0, or 0.1 to 1.0, or 0.2 to 5.0, or 0.2 to 2.0, or 0.2 to 1.0, or 0.3 to 5.0, or 0.3 to 2.0, or 0.3 to 1.0, or 0.4 to 5.0, or 0.4 to 2.0, or 0.4 to 1.0). Additionally or alternatively, the molar ratio of the organic additive to group 8 to 10 metals (e.g., Ni) may be 0.5 to 10 (e.g., 0.5 to 5.0, or 0.5 to 3.0, or 1.0 to 10, or 1.0 to 5.0, or 1.0 to 3.0).

[0056] If desired, additional materials, such as any materials that can be added during the preparation of conventional hydrogenation catalysts, may be added in addition to the metal components already added. Suitable examples of such additional materials include phosphorus compounds, boron compounds, fluorine-containing compounds, additional transition metals, rare earth metals, fillers, or any combination thereof.

[0057] In some embodiments, the catalyst further comprises a phosphorus compound. Suitable phosphorus compounds include ammonium phosphate, phosphoric acid, or organophosphorus compounds. The phosphorus compound can be added at any stage of the catalyst preparation process. The amount of phosphorus in the catalyst can be at least 1% by weight (calculated as P2O5) relative to the total weight of the catalyst, and more preferably in the range of 1 to 10% by weight (calculated as P2O5) relative to the total weight of the catalyst.

[0058] After the carrier is formed and then impregnated with metal, the carrier / catalyst composition is properly dried and calcined. The drying temperature can be in the range of 50°C to 200°C, and the drying time is preferably 0.5 to 5 hours. The calcination temperature can be in the range of 200°C to 800°C (e.g., 300°C to 600°C). Calcination of the carrier requires a relatively short time, for example, 0.5 to 3 hours. For calcination of the catalyst composition, controlled heating at a low heating rate may be required to ensure optimal dispersion of the metal. Such calcination may require 5 to 20 hours.

[0059] Before contact with hydrocarbon raw materials, the catalyst may be sulfided before use to form a metal sulfide catalyst. Sulfidation of the metal can be carried out by any convenient method, such as gas-phase sulfidation or liquid-phase sulfidation. Sulfidation is usually carried out by contacting a catalyst precursor (e.g., a catalyst precursor containing metal in the form of metal and / or metal oxide complexed with a dispersant) with a sulfur-containing compound (e.g., elemental sulfur, hydrogen sulfide, or polysulfide). Hydrogen sulfide is a convenient sulfiding agent for gas-phase sulfidation and can be added to a gas-phase sulfidation atmosphere containing 0.1% to 10% by weight of hydrogen. Sulfidation can also be carried out in the liquid phase using a combination of hydrogen and polysulfide, such as a dimethyl disulfide-added hydrocarbon stream. Sulfidation can be carried out at a convenient sulfidation temperature, e.g., 150°C to 500°C. Sulfidation can be carried out at a convenient sulfidation pressure, e.g., 100 psig to 1000 psig (689.5 kPa to 6.895 MPa) or higher. The sulfidation time may vary depending on the sulfidation conditions; therefore, a sulfidation time of 1 to 72 hours may be appropriate. The resulting catalyst may be steam-treated before use. [Examples]

[0060] The following exemplary embodiments are intended to be non-limiting.

[0061] Example 1 Production of jet boiling range hydrocarbons from n-octadecane The SSZ-41x catalyst was screened along with the MTW catalyst for the hydrogenation conversion of n-octadecane to hydrocarbons in the jet boiling point range. The catalysts were prepared by conventional methods. A mixed extruded substrate containing zeolite, alumina binder, and amorphous silica-alumina (ASA) was treated with NiCO3, citric acid, MoO3, and (NH4)6H2W. 12 O 40 The samples were co-impregnated with an aqueous solution containing H3PO4 and then calcined in air at 450°C for 60 minutes. The SiO2 / Al2O3 molar ratio of SSZ-41x was 75. The SiO2 / Al2O3 molar ratio of MTW zeolite (CBV8014, Zeolyst International) was 80-90. The catalyst properties are summarized in Table 1. [Table 1]

[0062] Catalyst performance was evaluated in a bench-scale unit operated in single-stage once-through mode under the conditions shown in Table 2. [Table 2]

[0063] Figure 1 is a graph showing the catalytic activity temperature (CAT) versus the hydrocracking (HCR) conversion rate (<500°F) during the hydrogenation of n-octadecane using SSZ-41x and MTW catalysts. As shown in the figure, over the range of synthetic HCR conversion rates tested (approximately 20-50% of <500°F), the difference in activity between catalysts containing MTW and SSZ-41 was approximately 5°F or less, averaging about 2°F. Therefore, the catalytic activity was substantially the same in terms of the accuracy of the test method. The results are summarized in Table 3. [Table 3]

[0064] Figure 2 is a graph of the product fraction yield against the HCR conversion rate during the hydrogenation of n-octadecan using the SSZ-41x catalyst and the MTW catalyst. As shown, the MTW catalyst and the SSZ-41 catalyst yielded nearly identical product yields for the jet (300°F~550°F), heavy naphtha (180°F~300°F), light naphtha (C5~180°F), and gas (C4-) across the range of conversion rates tested. The jet and gas yields are particularly interesting because they represent the most desired and least desired products, respectively. These results are summarized in Table 4. [Table 4]

[0065] Furthermore, if n-octadecane (normal boiling point, i.e., nBP = 603°F) is decomposed to produce n-C8 hydrocarbons (nBP = 257°F) or their lower products, compounds below the jet boiling point range (300°F to 550°F) are produced. Without being bound by any theory, the observation of high-yield jet product fractions relative to low-boiling point product fractions such as heavy naphtha (see, for example, Figure 2) suggests that n-octadecane was converted by the MTW and SSZ-41x catalysts, mainly or largely, by isomerization to species that boil within the jet range. This is a desirable result that demonstrates the feasibility of using MTW and / or SSZ-41x to selectively produce jet fuel from n-octadecane while avoiding excessive decomposition to less desirable light fractions.

[0066] Figure 3 is a graph of the freezing point of the jet product fraction against the HCR conversion rate during the hydrogenation of n-octadecan with MTW and SSZ-41x catalysts. The lowest freezing point detectable by the analytical methods used was -60°C. As shown in Figure 3, the freezing point of the jet fraction produced by the catalyst (300°F to 550°F) tends to decrease as the HCR conversion rate increases. In similar conversions, samples containing MTW produced jet fractions that solidified at lower temperatures than those produced by catalysts containing SSZ-41x, with the MTW and SSZ-41x catalysts yielding jet freezing points of -31.1°C and -5.4°C, respectively, with HCR conversion rates of 19.6% and 21.7% by weight, respectively.

[0067] Figures 4A and 4B are graphs of the cloud point and pour point of the jet product against the HCR conversion rate during the hydrogenation of n-octadecan using the SSZ-41x catalyst and the MTW catalyst, respectively. As shown in Figures 4A and 4B, the pour point / cloud point of the products boiling at 300°F+ and 500°F+ was generally lower with the catalyst containing MTW than with the SSZ-41x catalyst.

[0068] In summary, catalysts containing MTW and SSZ-41x generally yielded similar n-C18 HCR activity in terms of activity and product selectivity, although catalysts containing SSZ-41x were prepared to have significantly lower metal content than catalysts containing MTW. As a result, SSZ-41x may be overall more advantageous than MTW for the purpose of producing jet fuel from renewable raw materials, given its ability to yield comparable HCR yields with less metal overall and its lower propoxy hydrogenation activity. However, the freezing point of jet fuel produced by SSZ-41x is higher than that derived from MTW, which is generally less desirable. Catalysts containing either MTW zeolite or SSZ-41x zeolite demonstrate the ability to convert n-C18 to products in the boiling point range of 300°F–550°F with sufficiently high yield and satisfactory activity, and thus are suitable for producing jet fuel from renewable raw materials.

[0069] Example 2 Conventional production of middle distillates from petroleum raw materials The SSZ-41x catalyst was screened along with the MTW catalyst for the hydrogenation of unconverted oil (UCO) into hydrocarbons within the middle distillate boiling point range. The SSZ-41x catalyst and MTW catalyst were prepared as described in Example 1, except that the MTW zeolite (SAR=80) was prepared in-house. The catalyst characteristics are summarized in Table 2. [Table 2]

[0070] The petroleum raw material was unconverted oil (UCO) having the characteristics described in Table 6. [Table 6]

[0071] Catalyst performance was evaluated in a bench-scale unit operated in single-stage once-through mode under the conditions shown in Table 7. [Table 7]

[0072] Figure 5 is a graph showing the fraction yield against the HCR conversion rate during the hydrogenation of UCO using the MTW catalyst and the SSZ-41x catalyst. As shown in Figure 5, catalysts containing MTW and SSZ-41x yielded similar fraction yields (380°F to 700°F) across the range of conversion rates tested, with the MTW catalyst showing approximately 1% higher yield at any given conversion rate. These results are summarized in Table 8. [Table 8]

[0073] Figure 6 is a graph of the CAT to HCR conversion rates (<700°F) during the hydrogenation of UCO using the MTW catalyst and the SSZ-41x catalyst. As shown in Figure 6, the SSZ-41x catalyst showed significantly superior activity of approximately 18°F compared to the MTW catalyst within the range of HCR conversion rates tested. Although the yields of the fractions produced by each catalyst were relatively similar, SSZ-41x was substantially more advantageous in terms of activity (Figure 5). Generally, when one hydrogenation catalyst is significantly more active than another, it is accompanied by corresponding disadvantages such as lower HCR selectivity or lower product yield. In the specific case of the SSZ-41x catalyst, such disadvantages were disproportionately small, which suggests that SSZ-41x is inherently more advantageous than MTW in terms of activity.

[0074] In summary, both the MTW catalyst and the SSZ-41x catalyst were excellent at producing the middle distillate (boiling point 380°F to 700°F) with similar conversion rates and yields. However, the SSZ-41x catalyst was substantially superior to the MTW catalyst in terms of HCR activity.

Claims

1. A method for producing hydrocarbons within a fractional range, The process involves contacting a hydrocarbon raw material with a hydrogenation catalyst under hydrogenation conditions to produce a hydrogenated effluent, This includes fractionating the hydrogenated effluent to recover one or more hydrocarbon fractions that boil within the range of diesel fuel or jet fuel, The hydrogenation catalyst comprises a carrier component and a metal component supported on the carrier component, wherein the carrier component comprises (i) SSZ-41x zeolite in an amount of 0.1% to 75% by weight relative to the total weight of the carrier, (ii) amorphous silica-alumina in an amount of 15% to 85% by weight relative to the total weight of the carrier, and (iii) an alumina binder in an amount of 5% to 55% by weight relative to the total weight of the carrier, and the metal component comprises metals of Group 6 and non-precious metals of Groups 8 to 10, the method.

2. The method according to claim 1, wherein the hydrocarbon raw material contains at least 10% by weight of a biological component.

3. The method according to claim 2, wherein the biological component is obtained from the hydrodeoxygenation of renewable oil.

4. The method according to claim 1, wherein the hydrocarbon raw material comprises at least 40% by weight of n-paraffin.

5. The hydrogenation treatment conditions are a reaction temperature of 300°C to 500°C, a total pressure of 6 MPa to 30 MPa, a hydrogen supply rate of 800 SL / L to 2000 SL / L, and 0.1 h －１ ~10h －１ The method according to claim 1, including the liquid space velocity.

6. The aforementioned SSZ-41x zeolite has a SiO2 content of less than 30 to 100. ２ / Al ２ O ３ Molar ratio, and SiO2 between 15 and 75 ２ The method according to claim 1, having a molar ratio of / ZnO.

7. The method according to claim 1, wherein the SSZ-41x zeolite is present in an amount of 0.5% to 25% by weight relative to the total weight of the carrier.

8. The method according to claim 1, wherein the amorphous silica-alumina is present in an amount of 50% to 80% by weight relative to the total weight of the carrier.

9. Before being incorporated into the carrier, the amorphous silica-alumina has a total pore volume of 0.5 cm ３ / g to 2.0 cm ３ / g, an average pore diameter of 4 nm to 14 nm, and a BET surface area of 400 m ２ / g to 550 m ２ / g, and has one or more of the characteristics, and the method according to claim 1.

10. The method according to claim 1, wherein the alumina binder is present in an amount of 15% to 35% by weight relative to the total weight of the carrier.

11. The method according to claim 1, wherein the Group 6 metal is present in an amount of 5 to 40% by weight in terms of oxides relative to the total weight of the catalyst.

12. The method according to claim 1, wherein the metals of groups 8 to 10 are present in an amount of 1 to 10% by weight in terms of oxides relative to the total weight of the catalyst.

13. The method according to claim 1, wherein the metal of group 6 is selected from molybdenum and / or tungsten, and the metals of groups 8 to 10 are selected from cobalt and / or nickel.

14. The method according to claim 1, wherein the hydrogenation catalyst further comprises an organic dispersant having 2 to 10 carbon atoms and a ratio of the number of carbon atoms to the number of oxygen atoms of 0.6 to 2.

15. The method according to claim 14, wherein the organic dispersant is selected from citric acid, gluconic acid, nitrilotriacetic acid, ethylene glycol, or any combination thereof.

16. The hydrogenation catalyst is P ２ O ５ The method according to claim 1, further comprising phosphorus in an amount of 1 to 10% by weight.

17. The method according to claim 1, wherein the hydrogenation catalyst is further sulfurized under sulfurization conditions before contacting the hydrocarbon raw material with the hydrogenation catalyst.

18. The method according to claim 1, wherein the diesel fuel or jet fuel is used as a drop-in fuel composition or mixed with an existing fuel composition.

Images