Search

CN-122006798-A - Bio-based deoxidized oil hydroisomerization and cracking catalyst

CN122006798ACN 122006798 ACN122006798 ACN 122006798ACN-122006798-A

Abstract

The invention discloses a bio-based deoxidized oil hydroisomerization and cracking catalyst which comprises a modified SAPO-11 molecular sieve and active metal, wherein the preparation method of the modified SAPO-11 molecular sieve comprises the steps of mixing a silicon source, an aluminum source, water, auxiliary metal and a template agent to obtain initial gel, and obtaining the modified SAPO-11 molecular sieve after hydrothermal reaction, drying and roasting of the initial gel, wherein the auxiliary metal is one or more of chromium, zirconium and copper. The catalyst has low preparation cost and good thermal stability.

Inventors

  • Dai man
  • WANG DONGJUN
  • GAO SHAN
  • FENG SIHAN
  • ZU YU
  • GUO HONGYU
  • Zhao Chenkang
  • ZHAO GUANGHUI
  • GUO JINTAO
  • LIU YANFENG

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260512
Application Date
20241108

Claims (10)

  1. 1. A bio-based deoxidized oil hydroisomerization and cracking catalyst is characterized by comprising a modified SAPO-11 molecular sieve and active metal, wherein the preparation method of the modified SAPO-11 molecular sieve comprises the steps of mixing a silicon source, an aluminum source, water, auxiliary metal and a template agent to obtain initial gel, and obtaining the modified SAPO-11 molecular sieve after hydrothermal reaction, drying and roasting of the initial gel, wherein the auxiliary metal is one or more of chromium, zirconium and copper.
  2. 2. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 1 wherein the molar composition ratio of the initial gel is (0.5-2) M (0.05-0.25) K 2 O or Na 2 O (10-50) templating agent (0.01-0.05) Al 2 O 3 ：(0.5-1)SiO 2 ：(10-60)H 2 O, wherein M is a co-metal oxide.
  3. 3. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 1 or 2, wherein the template agent is one or more of1, 6-hexamethylenediamine, diethanolamine, diethylamine, n-butylamine.
  4. 4. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 1 wherein the active metal is Pt and/or Pd.
  5. 5. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 1 wherein the active metal is present in an amount of 0.3wt.% to 0.5wt.% on a single basis based on the mass of the molecular sieve.
  6. 6. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 1 wherein the hydrothermal reaction conditions are a reaction temperature of 120-200 ℃ and a reaction time of 8-36 hours.
  7. 7. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 1 wherein the calcination temperature during the preparation of the modified SAPO-11 molecular sieve is 400-600 ℃.
  8. 8. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 1 wherein the active metal is supported on the molecular sieve by impregnation.
  9. 9. The bio-based deoxygenated oil hydroisomerization and cracking catalyst of claim 8 further comprising the steps of drying and calcining after the active metal impregnation is completed.
  10. 10. The bio-based deoxidized oil hydroisomerization and cracking catalyst according to claim 9, wherein the drying condition after impregnation is 100-120 ℃ for 6-24 hours, and the roasting condition is 400-600 ℃ for 6-12 hours.

Description

Bio-based deoxidized oil hydroisomerization and cracking catalyst Technical Field The invention belongs to the technical field of catalysts, and particularly relates to a bio-based deoxidized oil hydroisomerization and cracking catalyst. Background The development of aviation industry is convenient for people to travel and promotes economic development, but simultaneously, the aircraft burns and consumes a large amount of CO 2 discharged by traditional fossil fuel, and the huge environmental problem is caused to the whole world. In order to cope with climate change, the international aviation assistant presents three promise targets of 'from 2009 to 2020, the average annual fuel efficiency is improved by 1.5%, the zero increase of carbon emission is realized in 2021-2035, and the carbon emission is reduced by 50% in 2050 compared with 2005' to the international civil aviation organization on behalf of the whole aviation industry. To achieve the emission reduction objective is difficult to achieve with existing fuel systems, and requires recourse to alternative technologies, aviation biofuels are among the most potential low carbon products. The aviation kerosene prepared from biomass oil generally adopts a two-step method, namely, the biomass oil or waste grease is converted into long-chain normal biological alkane (C16-C18) through reactions such as hydrogenation saturation, deoxidation, decarbonylation, decarboxylation and the like, and then hydrocracking/isomerization is carried out to obtain the aviation kerosene component (C9-C16). The core of the process route is the selection of the catalyst for the hydrocracking/isomerization reaction of long-chain normal biological alkane. At present, the research on hydrocracking/isomerization catalysts for long-chain normal paraffins (single hydrocarbon) from fossil energy sources is relatively more, while the research on hydrocracking/isomerization catalysts for mixed hydrocarbon from biomass is less, and the use of dual-function catalysts such as Pt/ZSM-5, pt/ZSM-22, pt/SAPO-11 and the like for hydrocracking/isomerization of long-chain normal biological paraffins has the defect of low yield or high cost of biological aviation kerosene. CN102876348a discloses a method for preparing biodiesel by hydrogenation. The vegetable oil is first hydrofined, the hydrofined effluent enters a gas-liquid separator above a hydrodewaxing reactor to separate gas from liquid, the separated refined oil is redistributed by a tower plate, and then passes through a hydrodewaxing catalyst bed in countercurrent with hydrogen, and the pour point depressing generated oil is separated to obtain the biodiesel product. The catalyst carrier is gamma-Al 2O3, which can collapse the catalyst structure under the long-term hydrothermal condition, reduce the specific surface area and pore volume and lower the mechanical strength. CN110862873a discloses a method for preparing hydrogenated biodiesel by catalyzing directional hydrodeoxygenation of grease, which belongs to the technical field of preparation of hydrogenated biodiesel. The hydrogenation biodiesel is prepared by adopting a molecular sieve supported catalyst, carrying out hydrodecarboxylation/decarbonylation on a catalytic grease raw material, wherein the total content of pentadecane and heptadecane in the hydrogenation biodiesel is more than 85%, the active component of the catalyst is Ni 2 P, the dosage of the catalyst is 5-10% of the weight of the reactive grease raw material, the main components of the hydrogenation biodiesel are pentadecane and heptadecane, the directional hydrodecarboxylation/decarbonylation selectivity is more than 80%, the generation of reaction water is reduced, the defect that the catalyst is easy to deactivate when meeting water is avoided, the service life of the catalyst is prolonged, the reaction conversion rate of the preparation of the hydrogenation biodiesel is more than 95%, the reaction energy consumption and the reaction cost are remarkably reduced, and the reaction temperature and the reaction time are greatly reduced. The catalyst is a molecular sieve supported catalyst, namely Ni 2 P/SAPO-11, and the existence of phosphide can cause a large amount of phosphating wastewater, the treatment cost is high, and the generated wastewater has serious pollution to the environment. CN103721741a proposes hydrodeoxygenation catalysts and hydroisomerization catalysts for the process of preparing biodiesel by hydrogenating castor oil and methods of use. The hydrodeoxygenation catalyst takes one of SAPO-11, ZSM-5 and gamma-Al 2O3 as a carrier, zn as an auxiliary agent and one of Ni and Ni 2 P, fe, pd, pt, moP, coP as an active component, the hydroisomerization catalyst takes one of SAPO-34, ZSM-22 and MCM-41 as a carrier, zn as an auxiliary agent and one or two of Ni and Ag as active components. In a high-pressure fixed bed reactor, castor oil undergoes hydrodeoxygenation reaction and hydroisomerization reaction, a