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CN-122010657-A - Preparation method of bio-based C17 normal alkane

CN122010657ACN 122010657 ACN122010657 ACN 122010657ACN-122010657-A

Abstract

The invention provides a preparation method of bio-based C17 normal alkane, which comprises the following steps of carrying out hydrodecarbonylation decarboxylation reaction on animal and vegetable oil under the action of a hydrodecarbonylation decarboxylation catalyst to obtain the bio-based C17 normal alkane, wherein the preparation method of the hydrodecarbonylation decarboxylation catalyst comprises the steps of 1, mixing magnesia-alumina spinel, tiO 2 and beta molecular sieve, grinding, then mixing with a binder, forming, roasting to obtain a catalyst carrier, and 2, loading an active component on the catalyst carrier to obtain the hydrodecarbonylation decarboxylation catalyst, wherein the mass ratio of magnesia-alumina spinel, tiO 2 and 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 (11)

  1. 1. The preparation method of the bio-based C17 normal alkane is characterized by comprising the following steps: animal and vegetable oil undergoes hydrodecarbonylation decarboxylation reaction under the action of a hydrodecarbonylation decarboxylation catalyst to obtain bio-based C17 n-alkane; the preparation method of the hydrodecarbonylation decarboxylation catalyst comprises 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 hydrodecarbonylation decarboxylation catalyst carrier; step 2, loading an active component on the hydrodecarbonylation decarboxylation catalyst carrier to obtain a hydrodecarbonylation decarboxylation 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 bio-based C17 normal alkane according to claim 1, wherein the method for preparing magnesium aluminate 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 bio-based C17 normal alkane according to claim 2, wherein magnesium salt, aluminum salt and acid solution are mixed to obtain solution A, template agent and water are mixed to obtain solution B, then the solution A and the solution B are mixed, and precipitant is added to carry out precipitation reaction to obtain precipitate.
  4. 4. The method for preparing bio-based C17 normal alkane according to claim 1, wherein at least one of sesbania powder, peptizing agent and dispersing agent is further added in step 1 for mixing, and the binder is pseudo-boehmite.
  5. 5. The preparation method of the bio-based C17 normal alkane, which is disclosed in claim 4, is characterized in that the mass ratio of the mixture of magnesia-alumina spinel, tiO 2 and beta molecular sieve 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 h.
  6. 6. The method for preparing the bio-based C17 normal alkane according to claim 1, wherein the active component is loaded on the hydrodecarbonylation decarboxylation catalyst carrier in a manner of impregnation, and the active component is molybdenum and nickel.
  7. 7. The method for preparing 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 preparation method of the bio-based C17 normal alkane according to claim 1, wherein the mass ratio of the active components in the hydrodecarbonylation decarboxylation catalyst is 20-30 parts by weight of metal oxide based on 100 parts by weight of the hydrodecarbonylation decarboxylation catalyst carrier, and 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.
  9. 9. The preparation method of the bio-based C17 normal alkane according to claim 1, wherein the active components in the hydrodecarbonylation decarboxylation catalyst are molybdenum and nickel, and the molar ratio of molybdenum to nickel is 0.10-0.3:1; before the animal and vegetable oil undergoes the hydrodecarbonyl decarboxylation reaction, the animal and vegetable oil undergoes the hydrofining reaction, and the preparation method of the hydrofining catalyst comprises 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 hydrofining catalyst carrier; step 2', loading the active components on the hydrofining catalyst carrier to obtain a hydrofining catalyst; 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, and in the hydrofining catalyst, the active components are molybdenum and nickel, and the molar ratio of the molybdenum to the nickel is 1-4:1.
  10. 10. The preparation method of the bio-based C17 normal alkane according to claim 9, wherein the animal and vegetable oil is at least one of castor oil, cotton seed oil, aleurites montana and palm oil, the temperature of the hydrodecarboxylation reaction is 300-400 ℃, the pressure is 1.5-3 MPa, the hydrogen oil volume ratio is 150-800:1, the temperature of the hydrofining reaction is 80-200 ℃, the pressure is 1.5-3 MPa, and the hydrogen oil volume ratio is 150-800:1.
  11. 11. The method for producing a bio-based C17 normal alkane according to claim 9, wherein the mass of molybdenum and nickel in the hydrodecarbonylation catalyst is 20 to 30 parts by mass based on MoO 3 and NiO based on 100 parts by mass of the hydrodecarbonylation catalyst support, and the mass of molybdenum and nickel in the hydrodepurification catalyst is 10 to 15 parts by mass based on MoO 3 and NiO based on 100 parts by mass of the hydrodepurification catalyst support.

Description

Preparation method of bio-based C17 normal alkane Technical Field The invention belongs to the field of chemical reagent production, and particularly relates to a preparation method of bio-based C17 normal alkane. Background 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. The industrialized normal alkane production raw material mainly comprises 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. CN200910100260 discloses a method for preparing alkane from higher fatty acid, which takes fatty acid methyl ester with 8-22 carbons as raw material, and carries out hydrodeoxygenation to produce alkane, but in the obtained product, most of carbon in fatty acid is removed, besides decarbonylation and decarboxylation reactions, other side reactions are also carried out, such as methyl stearate (methyl stearate) is taken as raw material, and under the condition that the conversion rate is at most 98%, the total yield of the obtained heptadecane and octadecane is only 75%. If ethyl stearate (ethyl stearate) is used as a raw material, the total yield of the obtained heptadecane and octadecane is only 82% under the condition that the conversion rate is up to 99%. CN201210322774 discloses a method for preparing alkane by hydrodeoxygenation of non-edible animal and vegetable oil, which uses a molybdenum-nickel catalyst containing 3-5wt% of cerium oxide and silicon oxide, wherein the main component of the product is C15-C18 mixed alkane, the alkane yield is about 82%, the C15-C18 mixed alkane yield is about 80%, decarbonylation and decarboxylation reactions are carried out in the prepared mixed arene, and C15 and C17 alkane are generated, and the selectivity is not high. CN202110518934 discloses a method for preparing high-purity C16 and C18 normal monoalkanes, which utilizes diluted vegetable oil to produce the high-purity C16 and C18 normal monoalkanes through double-bed hydrodeoxygenation reaction and rectification separation process, wherein a molybdenum nickel catalyst is filled