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CN-121991717-A - Deironing agent and preparation method and application thereof

CN121991717ACN 121991717 ACN121991717 ACN 121991717ACN-121991717-A

Abstract

The invention provides a deironing agent and a preparation method and application thereof, wherein the method comprises the steps of S1, mixing and kneading molecular sieve powder with alumina powder, carbon powder, a first surfactant, silica sol, ammonium phosphate and acid for 30-60min, forming and drying to obtain a precursor, S2, carrying out modification treatment on the precursor in a mixed aqueous solution of quaternary ammonium base and a second surfactant for 0.5-2h, roasting the obtained modified precursor to obtain the deironing agent, and further limiting the acid amount of the deironing agent. The iron removing agent prepared by the method can effectively remove inorganic iron and organic iron (especially iron petronate) in hydrocarbon raw materials, and high iron removing efficiency is realized.

Inventors

  • SU WU
  • SONG JUNNAN
  • ZHAO YUANSHENG
  • CUI RUILI
  • YANG XU
  • ZHANG BOHAN
  • ZHANG CHUNGUANG
  • ZHANG ZHIGUO
  • YU SHUANGLIN
  • CHENG TAO

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241101

Claims (11)

  1. 1. The preparation method of the deironing agent is characterized by comprising the following steps: s1, mixing and kneading molecular sieve powder, alumina powder, carbon powder, a first surfactant, silica sol, ammonium phosphate salt and acid for 30-60min, and then forming and drying to obtain a precursor; S2, modifying the precursor in a mixed aqueous solution of quaternary ammonium base and a second surfactant for 0.5-2 hours, and roasting the obtained modified precursor to obtain a deironing agent; wherein the concentration of the quaternary ammonium base in the mixed aqueous solution of the quaternary ammonium base and the second surfactant is 0.05-0.15mol/L; the weak acid central acid amount of the deironing agent is 1.3-2.7mmol/g, and the strong acid central acid amount is 0.3-0.7mmol/g.
  2. 2. The method according to claim 1, wherein in step S1, the amount of the alumina powder is 10% to 50%, the amount of the carbon powder is 35% to 45%, the amount of the first surfactant is 3% to 8%, the amount of the ammonium phosphate is 5% to 10%, the amount of the acid is 5% to 20%, and the amount of the silica sol is 1% to 5%, based on 100% of the dry mass of the molecular sieve powder.
  3. 3. The method of claim 1, wherein the quaternary ammonium base is used in an amount of 5% to 15% based on 100% dry weight of the molecular sieve powder.
  4. 4. The method of claim 1, wherein the concentration of the second surfactant in the aqueous mixture of the quaternary ammonium base and the second surfactant is from 0.1% to 0.3%.
  5. 5. The method of preparation of claim 1, wherein the first surfactant and the second surfactant are each independently selected from polyols; the ammonium phosphate salt is at least one selected from ammonium phosphate, monoammonium phosphate, diammonium phosphate and ammonium polyphosphate; The acid is at least one selected from nitric acid, acetic acid, oxalic acid, citric acid and salicylic acid; The quaternary ammonium base is selected from organic ammonium hydroxide having the general formula R 4 NOH, wherein each R is independently selected from a C1-C10 linear or branched alkyl group, or a C6-C10 aryl group; The molecular sieve powder is selected from at least one of molecular sieves with FAU framework structures, BEA topological framework structures, MFI framework structures and MWW framework structures.
  6. 6. The method of claim 1, wherein the firing temperature is 500-700 ℃ for a period of 6-10 hours; the drying temperature is 100-150 ℃ and the drying time is 1.5-2.5h.
  7. 7. The iron removing agent produced by the process for producing an iron removing agent according to any one of claims 1 to 6, wherein the iron removing agent has a total pore volume of 0.8 to 1.2cm 3 /g and a specific surface area of 150 to 300m 2 /g.
  8. 8. The deironing agent of claim 7, wherein the deironing agent comprises macropores greater than 50nm and wherein the pore volume of macropores greater than 50nm is between 10% and 20% of the total pore volume.
  9. 9. Use of a deironing agent obtainable by a process for the preparation of a deironing agent according to any one of claims 1 to 6 or a deironing agent according to claim 7 or 8 for the removal of iron from a hydrocarbonaceous feedstock.
  10. 10. A process for the de-ironing of a hydrocarbon feedstock comprising the steps of: Heating an iron-containing hydrocarbon raw material, then, entering a reactor filled with a deironing agent, and carrying out a deironing reaction under the conditions of inert atmosphere, 150-250 ℃ and airspeed of 0.5-2.0h -1 ; preferably, the reactor is selected from a fixed bed reactor and/or an upflow reactor.
  11. 11. The method of claim 10, wherein the iron-containing hydrocarbon feedstock is selected from at least one of distillate, crude oil, residuum, hydrogenated residuum, wax oil.

Description

Deironing agent and preparation method and application thereof Technical Field The invention relates to the technical field of heavy oil processing, in particular to a deironing agent and a preparation method and application thereof. Background In recent years, as the quality of crude oil becomes heavier and inferior, the processing amount of inferior crude oil is increasing. The Fe content in the crude oil is increased due to the change of the property of the crude oil and the corrosion of the crude oil in the process of pipe transportation and processing. However, the iron content of hydrocarbon feedstock is one of the main factors limiting the operating cycle time of hydrotreatment or hydrorefining units. Research shows that Fe element is different from other metal elements, and is difficult to enter into a protective agent or an internal pore canal of a hydrogenation agent after hydrogenation removal, and is deposited on the outer surface of a catalyst or a catalyst gap, so that the catalyst bed is easy to be blocked and hardened. It is counted that high Fe content in residuum hydrotreater process feedstock is one of the important reasons for causing the pressure drop in the first reactor to rise rapidly, approaching or exceeding the limit value of 0.7MPa, forcing the unit to shut down, and causing the catalyst in the downstream reactor to continue to function. The catalytic cracking process requires a higher Fe element content in the feedstock, generally requiring a Fe element content of no more than 5ppm in the feedstock. On one hand, fe element can pollute the FCC regeneration balancing agent, so that the micro-reactive activity of the balancing agent is obviously reduced under the condition of the same unit consumption, the total liquid yield of a product is reduced, the distribution of the product is poor, coke and dry gas are increased, the slurry oil yield is increased, and on the other hand, the specific gravity of the FCC catalyst is increased, fine powder scaling of the FCC catalyst occurs in the regeneration process, and the distribution and operation stability of the FCC product are seriously influenced. In industry, part of Fe element can be removed in the electric desalting link. However, the residual Fe element or the newly introduced Fe element during the processing of the hydrocarbon raw material can be enriched in the heavier distillate oil after passing through the atmospheric and vacuum system, and is difficult to remove. Aiming at the problem of iron removal in hydrocarbon raw materials, china patent document CN1107713C discloses a heavy and residual oil hydrotreating method, which achieves the effect of removing Fe element by adopting a section of adsorption filter bed or a section of adsorption filter bed and a section of adsorption filter catalyst bed to be used simultaneously before a heavy residual oil hydrotreating reaction system. However, the adsorption bed layer only depends on the filtration to remove iron-containing particles, the iron removal efficiency is low, the adsorption bed layer with adsorption and filtration catalyst is further matched, the Fe element removal is further realized under the high-pressure hydrogen atmosphere, the energy consumption is high, and the risk of blocking and hardening of the clinical layers is also high. Chinese patent document CN114806627A discloses a two-phase de-ironing method for hydrocarbon raw materials, wherein the hydrocarbon raw materials enter a de-ironing reaction zone and are sequentially contacted with a hydrogenation protective agent and a hydrodemetallization agent to react in the presence of a hydrogen-free atmosphere to obtain reaction effluent with reduced sulfur content and iron content, and the reaction depth is controlled to ensure that the difference of the sulfur content in the hydrocarbon raw materials before and after the reaction is less than 10 per the iron content in the hydrocarbon raw materials. In the method, a catalyst with hydrogenation performance is still used, but the hydrogenation is carried out in an atmosphere without introducing hydrogen, and a hydrocarbon raw material is used for supplying hydrogen to carry out shallow desulfurization and de-ironing reactors, so that the performance of the hydrogenation agent cannot be effectively exerted, on one hand, the cost is higher, and on the other hand, the bed pressure drop is still greatly increased along with the deposition of Fe element. In addition, the iron removal effect in the method is related to the desulfurization effect, the desulfurization rate is required to be improved to realize deep iron removal and is closely related to the sulfur content in the raw materials, but more C-S bond breakage can aggravate polycondensation among macromolecules in a hydrogen-free atmosphere, so that bed blockage is accelerated, and long-period operation of the device is not facilitated. Therefore, the existing effect of removing oil-soluble iron in hydrocarbon ra