Search

CN-117427605-B - Adsorbent for adsorbing, separating and removing aromatic hydrocarbon from diesel oil, preparation method and application thereof

CN117427605BCN 117427605 BCN117427605 BCN 117427605BCN-117427605-B

Abstract

The invention discloses a diesel oil dearomatization adsorbent, a preparation method and application thereof. The main component of the adsorbent is silicon dioxide, the main component is synthesized by hydrolysis reaction of organosilane and alcohols in water, after washing and drying, the particle size of the adsorbent can be controlled by adopting a rolling ball forming mode, the sphericity is high, the formed adsorbent is subjected to metal modification, the specific surface area of the modified adsorbent is large, the mass transfer rate is high, and the adsorbent is used for adsorbing and separating aromatic hydrocarbon components in diesel oil and has the advantages of large adsorption capacity and high aromatic hydrocarbon selectivity.

Inventors

  • JIANG ZHICHAO
  • WANG DEHUA
  • YANG YANQIANG
  • WANG HONGCHAO
  • LIU YUSI
  • WANG HUIGUO

Assignees

  • 中国石油化工股份有限公司
  • 中国石油化工股份有限公司石油化工科学研究院

Dates

Publication Date
20260505
Application Date
20220712

Claims (16)

  1. 1. A diesel oil dearomatization adsorbent, the preparation method of which comprises, (1) Under the acidic condition, the organosilane and the alcohol are subjected to hydrolysis reaction in water, and the hydrolysis product is polycondensed to generate silica sol; (2) Washing the silica sol with water, diluting, pulping, and spray drying to obtain silica powder; (3) Uniformly mixing silicon dioxide powder, a binder and an auxiliary agent, performing rolling ball forming, and selecting an adsorbent with the particle size of 60-100 meshes; wherein the BET specific surface area of the adsorbent is 600-750 m 2 /g, the micropore surface area at least accounts for 50% of the total surface area, the pore volume is 0.15-0.3 cm 3 /g, and the pore diameter is 2-3 nm.
  2. 2. The adsorbent according to claim 1, wherein the preparation method further comprises the steps of (4) and (5), namely (4) pre-acidifying the surface of the adsorbent, and (5) carrying out ion exchange on the pre-acidified surface of the adsorbent and a metal solution to obtain the metal-modified adsorbent for drying and activating.
  3. 3. The adsorbent according to claim 1, wherein in the step (1), an inorganic acid is added to an aqueous solution of an organosilane and an alcohol, and the pH is controlled to be in the range of 2 to 4, so that the hydrolysis product is polycondensed to form a sol.
  4. 4. The adsorbent according to claim 1, wherein the organosilane is one or more of tetramethoxysilane, tetraethoxysilane, methyl silicone oil and monosilane, the alcohol is one or more of methanol, ethanol and isopropanol, and the molar ratio of water to organosilicon is not less than 2.
  5. 5. The adsorbent according to claim 1, wherein in the step (2), the silica sol is washed, deionized water is added and mixed to prepare a silica aqueous slurry, spray drying is used to prepare powder, and 800-1000 mesh silica powder is selected by sieving.
  6. 6. The adsorbent according to claim 1, wherein in the step (3), 90 to 98 mass% of the silica powder, 1 to 5 mass% of the binder, and 0.1 to 5 mass% of the auxiliary agent are uniformly mixed and formed into a roll.
  7. 7. The adsorbent according to claim 6, wherein the binder is one or more of kaolin, halloysite and dickite, and the auxiliary agent is one or more of corn flour, starch, lignin and sesbania powder.
  8. 8. The adsorbent according to claim 2, wherein in the step (4), the adsorbent is mixed with an inorganic acid solution, stirred for 6 to 12 hours at 60 to 90 ℃, cooled, filtered, washed and dried.
  9. 9. The adsorbent according to claim 2, wherein in the step (5), the metal salt is dissolved in deionized water, the adsorbent is packed in an ion exchange column, ion exchange is performed at 80-95 ℃, and then drying and activation are performed under vacuum conditions.
  10. 10. The adsorbent according to claim 9, wherein the salt solution is one or more of sodium, potassium, magnesium, zinc, copper, strontium, silver and cesium salt solutions, and the concentration of metal ions is 0.1-0.6 mol/L.
  11. 11. The adsorbent according to claim 2, wherein the activation temperature is 80 to 180 ℃, and the ignition loss of the adsorbent at 600 ℃ after drying and activation is less than 25 mass%.
  12. 12. The adsorbent according to claim 2, wherein the adsorbent comprises 90 to 99 mass% of silica and 1 to 10 mass% of metal based on the total mass of the adsorbent.
  13. 13. The adsorbent according to claim 2, wherein the adsorbent comprises 93 to 98 mass% of silica and 2 to 7 mass% of metal based on the total mass of the adsorbent.
  14. 14. An adsorbent according to claim 12 or 13, wherein the metal is selected from one or more of sodium, potassium, magnesium, zinc, copper, strontium, silver, cesium.
  15. 15. The adsorbent of claim 1 or 2, wherein the adsorbent micropore surface area is 55% to 70% of the total surface area.
  16. 16. A method for adsorption separation and removal of aromatic hydrocarbon from diesel oil, wherein the adsorbent is the adsorbent according to any one of claims 1 to 15.

Description

Adsorbent for adsorbing, separating and removing aromatic hydrocarbon from diesel oil, preparation method and application thereof Technical Field The invention relates to a diesel oil dearomatization adsorbent and a preparation method thereof. Background The existing oil refining capacity is seriously excessive, and the problem of excessive finished oil, particularly diesel oil, is particularly remarkable. With the popularization of new energy automobiles, the problem of excessive oil products is further aggravated, so that the transformation of oil refining to chemical industry is becoming a trend. According to the principle of 'oil-suitable, alkene-suitable, aromatic-suitable, wetting-suitable, chemical-suitable', the petroleum processing process is known from the molecular level, hydrocarbon compounds with different structures are firstly separated and then processed and utilized, the value of each molecule is improved, not only petroleum resources can be fully and effectively utilized, but also the high-value chemical utilization of the oil can be realized, and the method has important significance in increasing the yield of chemicals such as ethylene, propylene and BTX with low cost, relieving the contradiction between supply and demand of finished oil, particularly diesel oil, and improving the economic benefit of a petroleum refining device. CN1600833a discloses a method for removing aromatic hydrocarbon in kerosene, which comprises the steps of contacting the kerosene with an adsorbent, using normal alkane of C5-C7 as a desorbent, realizing separation of aromatic hydrocarbon from alkane in the kerosene, and realizing yield increase of chemicals such as ethylene, BTX and the like by using the kerosene after removing aromatic hydrocarbon as a high-quality steam cracking raw material. CN108203595A discloses a method for extracting and separating aromatic hydrocarbon and alkane in diesel oil fraction, the diesel oil fraction is fed into extraction tower from lower portion, the extraction solvent is fed into extraction tower from upper portion, and passed through liquid phase extraction and extraction, the raffinate oil rich in alkane is removed from top portion of extraction tower, the rich solvent rich in aromatic hydrocarbon is fed into first vacuum distillation tower from bottom portion of extraction tower to make vacuum distillation, the solvent containing heavy aromatic hydrocarbon with higher boiling point is removed from bottom portion of first vacuum distillation tower and fed into upper portion of stripping tower, and the stripping agent is fed into stripping tower from lower portion so as to finally implement separation of aromatic hydrocarbon and alkane in diesel oil, and implement regeneration of extraction solvent. The extractant is ionic liquid and the anion isCompared with the methods such as diesel hydro-upgrading, the method has low energy consumption and no hydrogen consumption, but the ionic liquid has high price, so that the industrial popularization and application of the method are limited. CN111097376a discloses a molecular sieve for adsorbing normal paraffins, and a preparation method and application thereof, the method specifically comprises the steps of adopting a material containing naphthene to fully contact with a 5A molecular sieve, quickly heating to realize carbonization treatment of the molecular sieve, adopting a solvent of a chemical pore-expanding agent to impregnate the carbonized molecular sieve, drying and roasting to obtain a modified 5A molecular sieve, and separating naphtha into normal paraffins and non-normal paraffins by the modified molecular sieve, wherein the normal paraffins are high-quality steam cracking raw materials, and the non-normal paraffins are catalytic reforming raw materials, so that the comprehensive utilization value of the naphtha is improved. CN106475048a discloses a 5A molecular sieve type adsorbent without binder and a preparation method, wherein an alkali treatment mode is adopted to synthesize a NaA adsorbent without binder, and a Ca 2+ ion exchange mode is adopted to obtain a spherical adsorbent of 5A molecular sieve after roasting. The synthesized adsorbent has good strength and large burning base bulk density. The method is large and Kong Zhanbi less, can be used for the adsorption separation of normal alkane, and has high adsorption capacity and fast mass transfer. CN110938458a discloses a method for producing high quality industrial white oil, the method uses a simulated moving bed process, the raw material containing oil aromatic components is separated into an aromatic-rich extract and an alkane-rich raffinate after adsorption separation, the aromatic components are subjected to hydrogenation modification to increase BTX, and the alkane is used as the high quality industrial white oil. In summary, the conventional separation of normal hydrocarbon components, alkane components and arene components in naphtha, kerosene and diesel