Hydrocracking catalysts containing Ti and Zr substituted beta zeolite (*BEA) frameworks and their preparation and use

Abstract

The present invention relates to a process for hydrocracking or hydrotreating a hydrocarbon-containing feedstock, which comprises: * This is achieved by using a catalyst containing a BEA framework beta zeolite, where * A portion of the aluminum atoms in the BEA framework is substituted with 0.1 to 50 mass % each of Ti and Zr calculated on the basis of the oxides.

Description

[Technical field]

[0001] This application claims priority to U.S. patent application Ser. No. 16 / 589,719, filed Oct. 1, 2019, the contents of which are incorporated herein by reference in their entirety.

[0002] The present invention relates to a process for hydrocracking a hydrocarbon feedstock using a new catalytic composition, in particular a catalytic composition in which a portion of the aluminum ions in the zeolitic framework are replaced by 0.1 to 5 mass % of both titanium and zirconium, calculated on an oxide basis. * It comprises a BEA zeolite and also comprises at least one active phase metal having the function of hydrogenation and / or hydrodesulfurization and / or hydrodenitrogenation. [Background technology]

[0003] For many years, catalysts containing zeolites and one or both of titanium and zirconium, with the metals supported on the mesopores, have been used to treat bottom oils, see, for example, JP 2003-334305, JP 2002-255537, and JP 2003-226519, and see also U.S. Patents 10,293,332 and 9,221,036, which are incorporated herein by reference.

[0004] JP 2000-334305 A teaches hydrocracking catalysts comprising active phase metals on a zeolite support. The support comprises ultrafine particles of titanium oxide or zirconium oxide bound to the inner surfaces of the mesopores. The atomic ratio of Al to Si is 0.01-0.1, which corresponds to a SiO2 / Al2O3 molar ratio, or "SAR", of 20-200. These catalysts are prepared by mixing a mesopore-containing zeolite with an aqueous solution of Ti or Zr oxide at a pH of 0.8-2. The zeolite is then washed and calcined at 400-600°C.

[0005] The '255537' publication teaches a zeolite with high mesopore content and an atomic ratio of Al to Si of 0.01-0.2 (SAR of 10-200), 30-50% mesopore volume with pore diameter of 50-100 Å. The mesopores have a volume of 0.14 cc / g or more and 25% or more of the Al atoms are tetracoordinated. Ultrafine particles of Ti or Zr oxides, which are not easily reduced, are bonded to the inner surface of the zeolite mesopores. This acts as a support for the active phase metals. The process for making this catalyst is similar to that for the '334305' publication, in which the zeolite is contacted with an aqueous solution of Ti or Zr oxide at a pH of 0.8-2, then dried at 50-200°C and calcined at 350-600°C.

[0006] The '226519' application also teaches a hydrocracking catalyst in which the zeolite of FAU (faujasite) structure contains Ti, Zr, or Hf. The metal content is 0.1-10% by mass (calculated on an elemental basis), the Al / Si atomic ratio is 0.01-0.1 (SAR of 20-200), and further contains active phase metals. The FAU zeolite has a crystal lattice constant of 24.28-24.46 Å. Its preparation is similar to that of the above catalyst.

[0007] However, in these hydrocracking catalysts, the mesopores are blocked by metals present in the feedstock, e.g., vanadium and nickel, and therefore, these catalysts are not suitable for hydrotreating (i.e., hydrocracking) heavy hydrocarbon oils, e.g., VGO and DAO, or other petroleum-based hydrocarbon feedstocks, without a pre-protecting hydrodemetallization layer.

[0008] As disclosed in WO 2007 / 032232, the entirety of which is incorporated herein by reference, a hydrocracking catalyst containing a Y-type zeolite as a support contains titanium atoms incorporated into the zeolite framework. (In other words, a Y-type zeolite in which some of the aluminum atoms constituting the framework are replaced with titanium atoms) has been developed. The zeolite can be prepared by treating a Y-type zeolite with an acidic aqueous solution containing titanium and having a pH of 1.5 or less, followed by filtering, washing, and drying. This allows the zeolite to contain titanium atoms incorporated into the zeolite framework structure without clogging the mesopores. This reference states that when a hydrocracking catalyst containing the above-mentioned zeolite as a support is used to hydrocrack heavy hydrocarbon oils, the heavy hydrocarbon oils can be easily diffused into the mesopores, thereby improving the yield of middle distillates.

[0009] U.S. Patent No. 10,081,009, the disclosure of which is incorporated herein by reference in its entirety, teaches that USY zeolites having an FAU framework can be treated to replace a portion of the aluminum in their zeolite framework, where the aluminum is replaced with 0.1-5.0 wt. % Ti and Zr (both), the wt. % being calculated on an oxide basis. The resulting catalyst has been found to be very useful for hydrotreating and hydrocracking feedstocks, such as hydrocarbon oils. The catalyst provided high yields of middle distillates.

[0010] See also published U.S. Patent Application Publication No. 2015 / 0375218, which is also incorporated by reference in its entirety. U.S. Patent Application Publication No. 2013 / 0319910, which is also incorporated by reference in its entirety. All of these published patent applications use the backbone substituted USY catalysts discussed above.

[0011] Beta zeolites are known in the catalytic art, but not in the context of hydrotreating or hydrocracking. US Pat. No. 4,826,586, for example, teaches the possibility of using beta zeolites in the fluidized catalytic cracking (FCC) process. The conditions under which the FCC process is carried out are very different from those used in hydrocracking / hydrotreating, and those skilled in the art would not treat these processes as equivalent. The FCC process also does not use hydrogen, in contrast to hydrocracking / hydrotreating. See also CN106145136, as well as CN104549543 and CN106140289, which teach the modification of beta zeolites. In each case, the preparation method is that of ion exchange rather than framework substitution, whereby metals are incorporated into the zeolite, resulting in a catalyst that is not equivalent to one in which framework substitution has occurred.

[0012] US Patent No. 6,063,944 teaches the insertion of titanium into beta zeolite, but does not mention Zr. See also US Patent No. 6,017,840, which teaches the impregnation of metals into beta zeolite without framework substitution. Reddy et al., Studies in Surface Science and Catalysts, 94:309-316(1995) and Hamdy et al., Mol. Catalysts, 441:140-149(2017), and Raksh et al., J. Catalysis, 188:252-260 (1999), which discuss modification with Zr, but not Ti. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] JP 2003-334305 A [Patent Document 2] JP 2002-255537 A [Patent Document 3] JP 2003-226519 A [Patent Document 4] U.S. Pat. No. 10,293,332 [Patent Document 5] U.S. Patent No. 9,221,036 [Patent Document 6] JP 2000-334305 A [Patent Document 7] International Publication No. 2007 / 032232 [Patent Document 8] U.S. Patent No. 10,081,009 [Patent Document 9] US Patent Application Publication No. 2015 / 0375218 [Patent Document 10] US Patent Application Publication No. 2013 / 0319910 [Patent Document 11] U.S. Pat. No. 4,826,586 [Patent Document 12] China Patent Application Publication No. 106145136 [Patent Document 13] China Patent Application Publication No. 104549543 [Patent Document 14] China Patent Application Publication No. 106140289 [Patent Document 15] U.S. Patent No. 6,063,944 [Patent Document 16] U.S. Patent No. 6,017,840 [Non-patent literature]

[0014] [Non-Patent Document 1] Reddy et al., Studies in Surface Science and Catalysts, 94:309-316 (1995) [Non-Patent Document 2] Hamdy et al., Mol. Catalysts, 441:140-149 (2017) [Non-Patent Document 3] Rakshe et al., J. Catalysis, 188:252-260 (1999) Summary of the Invention [Problem to be solved by the invention]

[0015] It is an object of the present invention to provide a hydrocracking or hydrotreating process that improves the yield of desired products, such as middle distillates. [Means for solving the problem]

[0016] The object of the present invention is to produce a USY zeolite according to U.S. Pat. No. 10,081,009, which has an FAU framework, * This is achieved by substituting a beta zeolite with a BEA framework. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 shows XRD data to demonstrate the structural integrity of the catalyst of the present invention. [Diagram 2] FIG. 2 shows the UV-Vis spectra of the base zeolite and the final catalyst of the present invention. [Diagram 3] FIG. 3 graphically illustrates the difference in total acidity and acidity strength between the USY-based catalyst and the *BEA catalyst of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Detailed Description of the Preferred Embodiments The present invention is a process for hydrocracking a petroleum-based hydrocarbon feedstock under hydrocracking conditions using a catalyst, said catalyst comprising: *The catalyst comprises an active phase metal compound supported on a support comprising a beta zeolite having a BEA framework, wherein a portion of the aluminum atoms in the framework are substituted / replaced with 0.1-5 wt.% each of Ti and Zr, where the masses of Ti and Zr are calculated on an oxide basis. Optionally, in some cases, 0.1-5 wt.% Hf may also be used to replace Al. The active phase metals include one or more of Fe, Co, Ni, Rh, Pd, Ag, In, Pt, Au, Cr, Mo, or W. In some embodiments, the amount of Ti and Zr is 0.1-2.0 wt.% on an oxide basis. In further embodiments, the amount of Hf present is 0.1-2.0 wt.% on an oxide basis.

[0019] The modified beta zeolitic framework containing Ti and Zr atoms of the present invention preferably has one or more, most preferably all, of the following characteristics: (a) Crystal lattice constants of a = 1.260-1.270 nm, b = 1.260-1.270 nm, and c = 2.620-2.650 nm; (b) 400~800m 2 / g, preferably 500 to 700m 2 / g specific surface area, and (c) a molar ratio of SiO2 to Al2O3 of 10 to 200 (preferably 10 to 100, more preferably 30 to 70).

[0020] The "specific surface area" referred to above, as well as all other properties listed, refers to the modified zeolite itself. The zeolite-containing catalyst supports have a specific surface area of ​​15 to 500 m. 2 / g, more preferably 150 to 450m 2 / g.

[0021] In the hydrocracking catalyst for hydrocarbon oil according to the present invention, the specific surface area is preferably 15 to 500 m 2 / g, preferably 150 to 400m 2 / g; the volume of pores having a diameter of 600 Å or less is preferably in the range of 0.40-0.75 ml / g; and the amount of active phase metal component is in the range of 0.01-40 wt.%, preferably 10-35 wt.%, based on the oxide. The amount of TiZr beta zeolite in the catalyst is in the range of 1-80 wt.%, preferably 5-50 wt.%, based on the weight of the catalyst. In some embodiments, the catalyst is on an inorganic support, preferably an inorganic support comprising alumina and silica.

[0022] The method for producing a hydrocracking catalyst of the present invention includes the steps of: * The method includes a step of replacing a part of the aluminum atoms of a beta zeolite having a BEA framework with zirconium atoms and titanium atoms, and then calcining the zeolite at a temperature of 55 to 700° C. * Beta zeolites with a BEA framework have crystal lattice constants in the ranges of a = 1.260-1.270 nm, b = 1.269-1.270 nm, and c = 2.620-2.650 nm, and have a crystal lattice constants in the ranges of 400-800 nm. 2 The catalyst has a specific surface area of ​​100 / g and a molar ratio of SiO2 to Al2O3 of 10 to 200, preferably 10 to 100, and more preferably 30 to 70. A suspension having a liquid / solid mass ratio of 5 to 15 is prepared from the above-mentioned calcined zeolite, an inorganic acid or an organic acid is added thereto so that the pH of the suspension becomes less than 2.0, a zirconium compound and a titanium compound are then added, mixed, and the mixed solution is neutralized to obtain a catalyst.

[0023] In another method for producing the hydrocracking catalyst of the present invention, the above zeolite is used to prepare a suspension having a liquid / solid zeolite mass ratio of 5-15, an inorganic acid or an organic acid is added to the suspension so that the pH of the suspension is less than 2.0, a zeolite compound and a titanium compound are added and mixed, and then the mixed solution is neutralized to obtain a catalyst.

[0024] A third aspect of the present invention is a process for hydrocracking a petroleum-based hydrocarbon feedstock, such as a hydrocarbon oil, in the presence of hydrogen and under suitable reaction conditions using the hydrocracking catalyst described above.

[0025] Preferably, the method for hydrocracking a petroleum-based hydrocarbon feedstock according to the present invention comprises the steps of placing the catalyst of the present invention in a reaction vessel of a hydrocracker, which is a flow reactor, and carrying out the hydrocracking at a reaction temperature of 300° C. to 450° C., a hydrogen pressure of 4 to 30 MPa, and a reaction time of 0.1 to 10 h. -1 Liquid hourly space velocity (LHSV) and 500 to 2500 Nm 3 / m 3 The process includes treating a feedstock having a boiling point between 300°C and 833°C in the presence of hydrogen at a hydrogen / oil ratio of 0.1 to 0.5.

[0026] Preferably, the method for hydrocracking a hydrocarbon oil according to the present invention comprises hydrocracking a feedstock having a boiling point of 375 to 650° C. in the presence of a catalyst and hydrogen at a reactor temperature of 330° C. to 450° C., a hydrogen pressure of 7 to 15 MPa, and a pressure of 0.2 to 1.5 h. -1 Liquid hourly space velocity (LHSV) of 1000 to 2000 Nm 3 / m 3 to obtain a middle distillate, preferably enriched in kerosene and gas oil.

[0027] In the method for hydrocracking of hydrocarbon oil according to the present invention, the above-mentioned flow reactor (flow reactor) is preferably a flow reactor selected from the group consisting of a stirred bath reactor, a bubbling bed reactor, a baffled slurry bath reactor, a fixed bed reactor, a rotating tube reactor, and a slurry bed reactor.

[0028] In the method of hydrocracking a petroleum feedstock according to the present invention, the aforementioned hydrocarbon feedstock preferably includes (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sands, (5) Shell oil, or (6) refined oil obtained from liquefied coal.

[0029] In the method for hydrocracking of hydrocarbon oil according to the present invention, the aforementioned hydrocarbon oil comprises crude oil, synthetic crude oil, bitumen, oil sand, shell oil, or refined oil obtained from liquefied coal, and the refined oil is preferably any one of a) vacuum gas oil (VGO), b) deasphalted oil (DAO) or demetalized oil obtained from a solvent deasphalting process, c) light coker gas oil or heavy coker gas oil, d) cycle oil obtained from a fluid catalytic cracking (FCC) process, or e) gas oil obtained from a visbraking process.

[0030] The hydrocracking catalyst for hydrocarbon oil according to the present invention has a structure in which some of the aluminum atoms constituting the skeleton are substituted with zirconium atoms and titanium ions. * It comprises a hydrogenation metal component supported on a support comprising a beta zeolite of the BEA type.

[0031] Therefore, the hydrocracking catalyst of the present invention facilitates the diffusion of heavy hydrocarbons such as VGO, DAO, etc. into its mesopores compared to conventional hydrocracking catalysts.

[0032] FIG. 3 shows the results of tests to determine the acidity of catalysts of the present invention and of the prior art. EXAMPLES

[0033] Has a silica-to-alumina ratio (hereinafter "SAR") of 28.5 *A beta zeolite with a BEA framework was used. A total of 51.4 g of this zeolite was suspended in 450 g of deionized water and heated to 40° C. A total of 14.8 g of H2SO4 (25% by weight) was added together with 10.0 g of an aqueous titanium sulfate solution (corresponding to 5% by weight of TiO2). The solution contained 8.48 g of deionized water and 1.52 g of titanium sulfate (corresponding to 33% by weight of TiO2). An additional aqueous zirconium sulfate solution (2.8 g, constituting 18% by weight of ZrO2) was added and the mixture was stirred for 4 hours, then filtered and washed with 1.5 liters of deionized water. This was done at 60° C. The resulting zeolite was dried at 110° C. to obtain a framework-exchanged Ti / Zr beta zeolite.

[0034] Before and after skeletal replacement * XRD data for the BEA zeolite is shown in Figure 1. It can be seen that the structural integrity of the zeolite remains. EXAMPLES

[0035] * BEA zeolites and framework-substituted * The BEA zeolite was analyzed and the results are shown in Table 1.

[0036] [Table 1]

[0037] Additional data is shown in Figure 2, which shows the UV-Vis spectra of pristine and framework-substituted beta zeolites. A wavelength of about 250 nm is seen with the Ti 4-coordinate species. If the 6-coordinate species were present, a shift to higher wavelengths at about 285 nm would be expected. This did not occur as shown in Figure 2. EXAMPLES

[0038] Studies were carried out to determine how substitution of the alumina framework with Ti and Zr affects the acidity of the zeolite.

[0039] USY zeolite and * Both BEA zeolites were tested for acidity, unmodified, and modified with Ti and Zr substitutions.

[0040] Figure 3 shows these results, where the total acidity is indicated by the height of the bar, while the horizontal bars indicate the content of weak (100-200°C), medium (200-400°C), and strong (400-500°C) acid sites.

[0041] Other features of the invention will be apparent to those skilled in the art and need not be repeated here.

[0042] The terms and expressions which have been employed are used as terms of description and not of limitation, and in the use of such terms and expressions there is no intention of excluding equivalents of the features shown and described or portions thereof, recognizing that various modifications are possible within the scope of the invention.

Claims

1. 1. A process for hydrocracking or hydrotreating a hydrocarbon-containing feedstock, comprising: (i) subjecting the feedstock to a catalyst, the catalyst comprising an active phase metal and ＊ The beta zeolite of the BEA framework is included, ＊ a portion of the aluminum atoms in the BEA framework are replaced by 0.1 to 5.0 wt. % Ti atoms and 0.1 to 5.0 wt. % Zr atoms, said wt. % being calculated on an oxide basis; and (ii) contacting said feedstock with hydrogen to hydrocrack or hydrotreat said feedstock.

2. The method of claim 1, wherein the catalyst further comprises 0.1 to 5.0 wt. % Hf atoms, calculated on the oxide basis.

3. The beta zeolite has the following characteristics: (a) crystal lattice constants of a = 1.260-1.270 nm, b = 1.260-1.270 nm, and c = 2.620-2.650 nm; (b) 400-800m ２ / g specific surface area, and (c) 10 to 200, Al ２ O ３ SiO ２ The molar ratio of 2. The method of claim 1, comprising:

4. The β zeolite-containing catalyst carrier is 15 to 500 m ２ / g; a volume of pores having a diameter of 600 Å or less in the range of 0.40 to 0.75 ml / g; and an active phase metal content in the range of 0.01 to 40 wt. %.

5. A step of filling a reaction vessel, which is a flow reactor, with a hydrocracking catalyst; and a step of subjecting the reaction vessel to a reactor temperature of 300° C. to 450° C., a hydrogen pressure of 4 to 30 MPa, and a hydrolysis reaction of 0.1 to 10 h. －１ Liquid hourly space velocity (LHSV) of 500 to 2500 Nm ３ / m ３ 5. The process of claim 1, further comprising the step of processing a feedstock having a boiling point between 300° C. and 833° C. in the presence of hydrogen at a hydrogen / oil ratio of 0.1 to 0.5%.

6. 6. The method of claim 5, wherein the flow reactor is a flow reactor selected from the group consisting of a stirred bath reactor, an ebullated bed reactor, a baffled slurry bath reactor, a fixed bed reactor, a rotating tube reactor, and a slurry bed reactor.

7. 6. The method of claim 5, wherein the hydrocarbon oil comprises: (1) crude oil; (2) synthetic crude oil; (3) bitumen; (4) oil sands; (5) Shell oil; or (6) refined oil obtained from liquefied coal.

8. 6. The method of claim 5, wherein the hydrocarbon oil comprises crude oil, synthetic crude oil, bitumen, oil sands, shell oil, or refined oil obtained from liquefied coal, the refined oil being a) vacuum gas oil (VGO), b) deasphalted oil (DAO) or demetallized oil obtained from a solvent deasphalting process, c) light coker gas oil or heavy coker gas oil obtained from a coker process, d) cycle oil obtained from a fluid catalytic cracking (FCC) process, or e) gas oil obtained from a visbreaking process.

9. A step of filling a hydrotreating device, which is a flow reactor, with a hydrocracking catalyst; and a step of subjecting a feedstock having a boiling point of 375 to 650°C to a hydrogen cracking process in the presence of hydrogen at a reactor temperature of 330°C to 450°C under a hydrogen pressure of 7 to 15 MPa for 0.2 to 1.5 h. －１ Liquid hourly space velocity (LHSV) of 1000 to 2000 Nm ３ / m ３ to obtain a middle distillate fraction.

10. The method according to any one of claims 1 to 4, wherein the beta zeolite contains 0.1 to 2.0 mass% each of Ti and Zr on an oxide basis.

11. 3. The method of claim 2, wherein the beta zeolite contains 0.1 to 2.0 wt. % Hf on an oxide basis.

12. The process according to any one of claims 1 to 4, wherein the catalyst is present on an inorganic support.

13. The method of claim 12, wherein the inorganic support comprises at least one selected from the group consisting of alumina and silica.

14. The beta zeolite is Al ２ O ３ SiO ２ The process according to any one of claims 1 to 4, wherein the molar ratio of

15. The method of claim 14, wherein the molar ratio is from 30 to 70.

16. The specific surface area is 500 to 700 m ２ The method of claim 3, wherein the molecular weight is 1 / g.

17. The catalyst is 150 to 500 m ２ The method according to claim 12, wherein the specific surface area is 0.1-0.25 μm / g.

18. The specific surface area is 150 to 450 m ２ The method of claim 17, wherein the molecular weight is 1 / g.

19. A process according to any one of claims 1 to 4, wherein the active phase metal component constitutes from 0.01 to 40% by weight of the catalyst, calculated on an oxide basis.

20. 20. The method of claim 19, wherein the active phase metal component comprises 10 to 35 mass % of the catalyst, calculated on an oxide basis.

21. 5. The method of claim 1, wherein the active phase metal comprises Fe, Co, Ni, Rh, Pd, Ag, In, Pt, Au, Cr, Mo, or W.

22. The process of any one of claims 1 to 4, wherein the beta zeolite constitutes 1 to 80% by weight of the catalyst.

23. 23. The method of claim 22, wherein the beta zeolite comprises 5 to 50% by weight of the catalyst.

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