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CN-122006794-A - Catalyst for preparing bio-based C17 normal alkane and preparation method thereof

CN122006794ACN 122006794 ACN122006794 ACN 122006794ACN-122006794-A

Abstract

The invention provides a catalyst for preparing bio-based C17 normal alkane and a preparation method thereof, and the catalyst comprises the following steps of 1, mixing magnesia-alumina spinel, tiO 2 and beta molecular sieve, grinding, then mixing with pseudo-boehmite and sesbania powder, forming, roasting to obtain a catalyst carrier, and 2, loading active components on the catalyst carrier to obtain the catalyst, wherein the mass ratio of the magnesia-alumina spinel, the TiO 2 and the beta molecular sieve is 100:0.05-0.5:1.0-5.0. According to the invention, tiO 2 , the beta molecular sieve and the magnesia-alumina spinel are mixed and modified, so that the prepared catalyst has higher conversion rate and higher normal alkane selectivity when being used for preparing the bio-based C17 normal alkane from animal and vegetable oil.

Inventors

  • JIA YUNGANG
  • WANG GANG
  • ZHANG TIEZHEN
  • JI YONGGANG
  • XIA ENDONG
  • LI RUIFENG
  • MA SHOUTAO
  • GUAN XU
  • WANG ZIDONG
  • SUN FAMIN

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260512
Application Date
20241112

Claims (10)

  1. 1. A method for preparing a catalyst for preparing bio-based C17 normal alkane, which is characterized by comprising the following steps: Step 1, mixing magnesia-alumina spinel, tiO 2 and beta molecular sieve, grinding, then mixing with a binder, forming and roasting to obtain a catalyst carrier; step 2, loading an active component on the catalyst carrier to obtain a catalyst; wherein the mass ratio of the magnesia-alumina spinel to the TiO 2 to the beta molecular sieve is 100:0.05-0.5:1.0-5.0.
  2. 2. The method for preparing the catalyst for preparing the bio-based C17 normal alkane according to claim 1, wherein the method for preparing the magnesia-alumina spinel comprises the following steps: Mixing magnesium salt, aluminum salt and template agent to form solution, carrying out precipitation reaction by using a precipitator to obtain precipitate, and drying and roasting the precipitate to obtain the magnesia-alumina spinel.
  3. 3. The method for preparing the catalyst for preparing the bio-based C17 normal alkane according to claim 2, wherein the magnesium salt, the aluminum salt and the acid solution are mixed to obtain a solution A, the template agent and water are mixed to obtain a solution B, then the solution A and the solution B are mixed, and a precipitant is added to carry out precipitation reaction to obtain a precipitate.
  4. 4. The method for preparing a catalyst for preparing bio-based C17 n-alkanes according to claim 1, wherein step 1 is further mixed with at least one of sesbania powder, peptizing agent and dispersing agent, and the binder is pseudo-boehmite.
  5. 5. The preparation method of the catalyst for preparing the bio-based C17 normal alkane, which is disclosed in claim 4, is characterized in that the mass ratio of the magnesium aluminate spinel, the TiO 2 and the beta molecular sieve mixture to the binder is 60:30-50:1-5, the peptizing agent is aqueous nitric acid solution, the dispersing agent is aqueous citric acid solution, the roasting temperature in step 1 is 450-550 ℃, and the roasting time is 4-6 hours.
  6. 6. The method for preparing a catalyst for preparing bio-based C17 n-alkanes according to claim 1, wherein the active components are molybdenum and nickel, and the active components are supported on the catalyst carrier in a manner of impregnation.
  7. 7. The method for preparing the catalyst for preparing the bio-based C17 normal alkane according to claim 6, wherein the molar ratio of molybdenum to nickel is 0.15-0.25:1, and the roasting time is 4-8 hours at the roasting temperature of step 2 of 500-600 ℃.
  8. 8. The method for preparing the catalyst for preparing the bio-based C17 normal alkane according to claim 1, wherein the mass of the active component in the catalyst is 20-30 parts by mass of metal oxide based on 100 parts by mass of the total mass of the catalyst carrier.
  9. 9. The method for preparing the catalyst for preparing the bio-based C17 normal alkane, according to claim 1, wherein the mass ratio of the magnesia-alumina spinel, the TiO 2 and the beta molecular sieve is 100:0.1-0.2:1.5-2.5.
  10. 10. A catalyst obtainable by the process of any one of claims 1 to 9.

Description

Catalyst for preparing bio-based C17 normal alkane and preparation method thereof Technical Field The invention belongs to the field of catalytic materials, and particularly relates to a catalyst for preparing bio-based C17 normal alkane and a preparation method thereof. Background Normal paraffins are known as liquid paraffin because they are transparent and colorless or pale yellow liquids at normal temperature. According to the fractions, light liquid paraffin (light paraffin for short, C9-C13) and heavy liquid paraffin (heavy paraffin for short, C14-C16) can be classified. The C15-C18 normal alkane is mainly used for phase change materials, and is used for controlling the temperature of medical cold-chain logistics, phase change energy storage buildings, phase change microcapsules for textiles and electronic components. The solvent can also be used for separating and analyzing lower hydrocarbon, dewaxing solvent, machining oil, base oil for special rust-proof oil, metal machining base oil, metal cleaning agent, gas chromatography reference substance and fixing liquid. And can also be applied to the gas storage functions of hydrogen storage, nitrogen storage and the like. N-heptadecane has wide application in the fields of functional temperature-regulating textiles and building energy conservation and cold chain transportation. As a phase change material, the n-heptadecane has a phase change temperature of 22 ℃, the purity of 99.7-99.9%, and the enthalpy value of 218J/g. N-heptadecane can be used as a phase change material for preparing heptadecane dibasic acid by fermentation, the heptadecane dibasic acid can be used for artificially synthesizing precious spice, namely, a civet, which is one of the indispensable raw materials in high-grade essence and flavored products in the spice industry, and has the functions of precious and fine animal-type aroma and aroma fixation and aroma preservation, so that the civet is regarded as an indispensable treasure in fine-flavor flavoring of cosmetics for famous perfumers in the world. N-heptadecane is also an environment-friendly, renewable, pure plant-extracted natural pollution-free nonpolar organic solvent, is particularly suitable for application products for attaching to skin and the application of ointment, is an excellent substitute for mineral oil, and has the characteristics of luster, lubrication, skin moistening and no greasy feeling. Cosmetic applications include creams and lotions, make-up, shampoos (shampoos, conditioners, styling lotions), deodorants, sunscreens and lotions, make-up removers, body washes, hand washes/soaps. In industrialization, raw materials for producing normal paraffins mainly comprise petroleum wax and Fischer-Tropsch synthetic oil wax. When normal paraffins are produced by petroleum wax and Fischer-Tropsch synthetic oil wax, because the normal paraffins contain complex components such as olefins, isoparaffins, naphthenes, aromatic hydrocarbons, oxygen-containing compounds, sulfur-containing compounds, nitrogen-containing compounds and the like, the normal paraffins and the isoparaffins need to be removed and purified through the processing procedures such as deep hydrofining, rectification, normal/isoparaffin separation and the like, and the production process is complex and the process conditions are harsh. Besides the production of monomer normal paraffins by using petroleum wax and Fischer-Tropsch synthetic oil wax as raw materials, the production of monomer normal paraffins by hydrodeoxygenation of animal and vegetable oil esters has the problems of low conversion rate of animal and vegetable oil into monomer paraffins, low decarbonylation and decarboxylation selectivity, C16, C18 and other byproducts in products. CN201810834967 discloses a preparation method of vegetable oil hydrodeoxygenation catalyst, mgAl 2O4 powder, aluminum hydroxide dry gel and sesbania powder are uniformly mixed, extruded, shaped and roasted to obtain catalyst carrier, nickel-molybdenum active component is loaded, secondary biodiesel is produced, the deoxidation conversion rate is close to 100%, n-pentadecane and n-heptadecane are produced as side reaction products, and the selectivity of n-pentadecane and n-heptadecane is not high. CN202110942495 discloses a water-resistant core-shell catalyst for hydrodeoxygenation of vegetable oil, which is obtained by assembling a shell structure of Ni-Al-Mo 7O246- LDHs on the surface of alumina to obtain a core-shell catalyst of Ni-Mo/gamma-Al 2O3, and has greatly improved water-resistant stability and mild reaction conditions in hydrodeoxygenation reaction of a vegetable oil model compound methyl palmitate. However, in the hydrodeoxygenation reaction, when the deoxidation conversion rate reaches 86%, n-pentadecane appears as a side reaction product, the selectivity is only 45%, and the selectivity of n-pentadecane is not high, so that a large amount of n-hexadecane is generated. CN105944750B discloses a high-se