Search

KR-102961248-B1 - Hydrocracking catalyst comprising a beta zeolite (*BEA) framework substituted with Ti and Zr, and methods for preparing and using the same

KR102961248B1KR 102961248 B1KR102961248 B1KR 102961248B1KR-102961248-B1

Abstract

The present disclosure relates to a method for hydrocracking or hydrogenating a hydrocarbon-containing feedstock. The method is achieved by using a catalyst comprising a β-zeolite of a *BEA framework, wherein some of the aluminum atoms in the *BEA framework are substituted with 0.1 to 5.0 wt% each of Ti and Zr calculated on an oxide basis.

Inventors

  • 호지킨스, 로버트, 피터
  • 코서글루, 오메르, 레파
  • 우치다, 코지
  • 가가와, 토모야스
  • 와타베, 미츠노리

Assignees

  • 사우디 아라비안 오일 컴퍼니
  • 니끼 쇼꾸바이 카세이 가부시키가이샤
  • 재팬 쿠퍼레이션 센터 포 페트로리움 앤드 서스테이너블 에너지

Dates

Publication Date
20260508
Application Date
20200924
Priority Date
20191001

Claims (20)

  1. As a method for the hydrocracking of a hydrocarbon-containing feedstock, A method for hydrocracking a hydrocarbon-containing feedstock, comprising the step of contacting the feedstock with (i) a catalyst and (ii) hydrogen to hydrocracking the feedstock, wherein the catalyst comprises an active phase metal and a β-zeolite of a *BEA framework, wherein some of the aluminum atoms in the *BEA framework are substituted with 0.1 to 5.0 wt% of Ti atoms and 0.1 to 5.0 wt% of Zr atoms, and said wt% is calculated based on oxides.
  2. In claim 1, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the catalyst further comprises 0.1 to 5.0 weight% of Hf atoms calculated based on oxides.
  3. In claim 1, A method for the hydrocracking of a hydrocarbon-containing feedstock, wherein the above β-zeolite has the following characteristics: (a) Crystal lattice constants of a = 1.260 to 1.270 nm, b = 1.260 to 1.270 nm and c = 2.620 to 2.650 nm, (b) a specific surface area of 400 to 800 m²/g, and (c) Molar ratio of SiO2 to Al2O3 of 10 to 200 .
  4. In claim 1, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the above β-zeolite-containing catalyst has a specific surface area of 15 to 500 m²/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 amount of active phase metal component in the range of 0.01 to 40 mass%.
  5. In any one of claims 1-4, A step of filling a reactor vessel, which is a fluidized reactor, with a hydrocracking catalyst; and A method for hydrocracking a hydrocarbon-containing feedstock, further comprising the step of treating a feedstock having a boiling point of 300°C to 833°C in the presence of hydrogen at a reactor temperature of 300°C to 450°C, a hydrogen pressure of 4 to 30 MPa, a liquid space velocity (LHSV) of 0.1 to 10 h⁻¹, and a hydrogen/oil ratio of 500 to 2500 Nm³/m³.
  6. In claim 5, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the above-mentioned fluidized reactor is selected from the group consisting of a stirred-bed type reactor, an ebullient bed reactor, a baffle-equipped slurry bath type reactor, a fixed-bed reactor, a rotating tubular reactor, and a slurry bath reactor.
  7. In claim 5, Hydrocarbon oil is a method of hydrocracking a hydrocarbon-containing feedstock, comprising (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sand, (5) shale oil, or (6) refined oil obtained from coal oil.
  8. In claim 5, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the hydrocarbon oil comprises refined oil obtained from crude oil, synthetic crude oil, bitumen, oil sands, shale oil, or coal oil, and said refined oil is a) vacuum gas oil (VGO), b) deasphalted oil (DAO) or demetaled oil obtained from a solvent deasphalting process, c) light coker gas oil or heavy coker gas oil obtained from a coker process, d) circulating oil obtained from a fluid catalytic cracking (FCC) process, or e) gas oil obtained from a bisbraking process.
  9. In any one of claims 1-4, A method for hydrocracking a hydrocarbon-containing feedstock, further comprising: a step of filling a hydrocracking catalyst into a hydrocracking treatment device which is a fluidized reactor; and a step of treating a feedstock having a boiling point of 375°C to 650°C in the presence of hydrogen at a reactor temperature of 330°C to 450°C, a hydrogen pressure of 7 to 15 MPa, a liquid space velocity (LHSV) of 0.2 to 1.5 h⁻¹ , and a hydrogen/oil ratio of 1000 to 2000 Nm³ /m³ to obtain an intermediate distillate.
  10. In any one of claims 1-4, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the above β-zeolite contains 0.1 to 2.0 mass% of Ti and Zr, respectively, based on oxides.
  11. In claim 2, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the above β-zeolite contains 0.1 to 2.0 mass% Hf based on oxides.
  12. In any one of claims 1-4, The above catalyst is a method for the hydrocracking of a hydrocarbon-containing feedstock on an inorganic support.
  13. In claim 12, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the above-mentioned inorganic support comprises at least one of alumina and silica.
  14. In any one of claims 1-4, The above β-zeolite is a method for hydrocracking a hydrocarbon-containing feedstock having a molar ratio of SiO2 to Al2O3 of 10 to 100 .
  15. In claim 14, A method for the hydrogenation cracking of a hydrocarbon-containing feedstock, wherein the above molar ratio is 30 to 70.
  16. In claim 3, A method for hydrocracking a hydrocarbon-containing feedstock having a specific surface area of 500-700 m²/g.
  17. In claim 12, The above catalyst is a method for the hydrocracking of a hydrocarbon-containing feedstock having a specific surface area of 150-500 m²/g.
  18. In claim 17, A method for hydrocracking a hydrocarbon-containing feedstock having a specific surface area of 150-450 m²/g.
  19. In any one of claims 1-4, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the active phase metal component comprises 0.01-40 mass% of the catalyst calculated based on oxides.
  20. In claim 19, A method for hydrocracking a hydrocarbon-containing feedstock, wherein the active phase metal comprises 10-35 mass% of the catalyst calculated based on oxides.

Description

Hydrocracking catalyst comprising a beta zeolite (*BEA) framework substituted with Ti and Zr, and methods for preparing and using the same This application claims priority to U.S. Patent Application No. 16/589,719, filed on October 1, 2019, the contents of which are incorporated herein by reference in their entirety. The present invention relates to a method for hydrocracking a hydrocarbon feedstock using a novel catalyst composition. Specifically, the catalyst composition comprises *BEA zeolite, wherein some of the aluminum ions within the zeolite framework are substituted with both titanium and zirconium in an amount of 0.1-5 mass% calculated on an oxide basis, and also comprises at least one active phase metal having a hydrogenation and/or hydrodesulfurization and/or hydrodenitrification function. For many years, zeolites in which metals are supported in the mesopores, and catalysts containing either titanium or zirconium have been used for bottom oil treatment. See, for example, Japanese unexamined patent applications No. 2000-334305, No. 2002-255537, and No. 2003-226519. Also, refer to U.S. patents No. 10,293,332 and No. 9,221,036 incorporated by reference. Japanese Patent Application Publication No. 2000-334305 discloses a hydrocracking catalyst comprising an active phase metal on a zeolite support. The support comprises ultrafine particles of titanium or zirconium oxide bonded to the inner surface of mesopores. The atomic ratio of Al to Si is 0.01-0.1, which corresponds to a SiO₂ / Al₂O₃ molar ratio or a "SAR" of 20 to 200. Such a catalyst is prepared by bonding the mesopores containing the zeolite with an aqueous solution of Ti or Zr oxide at a pH of 0.8 to 2. Next, the zeolite is washed, dried, and calcined at 400 to 600°C. The above publication "255537" teaches a zeolite having a high mesopore content, an atomic ratio of Al to Si of 0.01 to 0.2 (SAR 10 to 200), and 30 to 50 percent of the mesopore volume having a pore diameter of 50 to 100 Å. The mesopores have a volume of 0.14 cc/g or more, and 25 percent or more of the Al atoms are tetracoordinated. Ultrafine particles of Ti or Zr oxide that are not easily reduced are bonded to the inner surface of the zeolite mesopores. This acts as a support for the active phase metal. The catalyst preparation process is similar to the application of "334305" in that the zeolite is contacted with an aqueous solution of Ti or Zr oxide at pH 0.8 to 2, then dried at 50 to 200°C and calcined at 350 to 600°C. The above application "226519" also teaches a hydrocracking catalyst in which a faujasite (FAU) structured zeolite contains Ti, Zr, or Hf. The metal content is 0.1 to 10 wt% (calculated on an elemental basis), the Al/Si atomic ratio is 0.01 to 0.1 (SAR 20 to 200), and the active phase also contains metal. The crystal lattice constant of the FAU zeolite is 24.28 to 24.46 Å. The preparation is similar to that of the catalyst described above. However, these hydrocracking catalysts were not suitable for the hydrotreatment (or hydrocracking) of heavy hydrocarbon oils such as VGO and DAO, or other petroleum-based hydrocarbon feedstocks (where there is no pre-protected hydrodemetallization layer) because the pores were clogged by metals present in the feedstock, such as vanadium and nickel. As disclosed in WO 2007/032232, the entirety of which is incorporated by reference, a hydrocracking catalyst comprising a Y-type zeolite as a support contains titanium atoms incorporated into the zeolite framework (i.e., a Y-type zeolite in which some of the aluminum atoms constituting the framework are replaced with titanium atoms). The zeolite can be prepared by treating the Y-type zeolite with an acidic aqueous solution containing titanium with a pH of 1.5 or lower, followed by filtration, washing, and drying. By doing so, the zeolite can be prepared to contain titanium atoms incorporated into the zeolite framework structure without blocking the mesopores. The aforementioned reference states that when a heavy hydrocarbon oil is hydrocracking using a hydrocracking catalyst comprising the zeolite as a support, the yield of the intermediate distillate is improved because the heavy hydrocarbon oil diffuses easily into the mesopores. U.S. Patent No. 10,081,009 (the entire disclosure of which is incorporated by reference) teaches that USY zeolite having a FAU framework can be treated to replace a portion of aluminum in the zeolite framework, said aluminum can be substituted with 0.1 to 5.0 wt% of Ti and Zr, where weight% is calculated on an oxide basis. The resulting catalyst was found to be very useful for the hydrogenation and hydrocracking of feedstocks such as hydrocarbon oils. The catalyst provided a high yield of intermediate distillate. Also, refer to U.S. Patent Publication No. US 2015/0375218, the entirety of which is incorporated by reference. U.S. Patent Publication No. US 2013/0319910 is also incorporated by reference. All of these published patent applications use a USY