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CN-110961124-B - Hydrogenation olefin removal catalyst for reformate, preparation method and application

CN110961124BCN 110961124 BCN110961124 BCN 110961124BCN-110961124-B

Abstract

A catalyst for hydrodeolefine in reforming oil comprises an alumina carrier containing sulfate radical and active components calculated by taking alumina as a reference, wherein the content of the sulfate radical in the alumina carrier containing the sulfate radical is 0.22-0.40 mass percent, 0.07-0.18 mass percent of Pt and 0.4-3.0 mass percent of chlorine, and the content of the sulfate radical in the alumina carrier containing the sulfate radical is calculated by taking alumina as a reference and is 0.3-3.0 mass percent. The catalyst can effectively remove olefin in the reformed oil with bromine index higher than 4000mgBr/100g oil, the catalyst does not need to be presulfided before use, and the olefin-removed product with bromine index lower than 50mgBr/100g oil can be obtained, and the aromatic hydrocarbon loss is lower than 0.5 mass percent.

Inventors

  • WANG TAO
  • ZANG GAOSHAN
  • ZHANG YUHONG
  • WANG JIAXIN
  • YU NING

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
20180928

Claims (16)

  1. 1. A catalyst for hydrodeolefination of reformate comprises an alumina carrier containing sulfate radicals and the following active components calculated by taking alumina as a reference: pd0.22 to 0.40 mass%, 0.07 To 0.18 mass% of Pt0, 0.4 To 3.0 mass% of chlorine, The sulfate radical content in the sulfate radical-containing alumina carrier is 0.3-3.0 mass percent based on alumina, and the mass ratio of Pd/Pt in the catalyst is 2.2-6.0:1.
  2. 2. Catalyst according to claim 1, characterized in that the active component content of the catalyst is as follows: pd0.22 to 0.30 mass%, 0.07 To 0.15 mass% of Pt0, 0.4 To 2.0 mass% of chlorine, The sulfate radical content in the sulfate radical-containing alumina carrier is 0.4-2.0 mass percent calculated by taking alumina as a reference.
  3. 3. Catalyst according to claim 1 or 2, characterized in that the Pd and Pt are homogeneously dispersed in the support and the sodium content in the catalyst is not higher than 0.05 mass%.
  4. 4. The catalyst according to claim 1 or 2, characterized in that the specific surface area of the sulfate-containing alumina carrier is 180-300 m 2 /g and the pore volume is 0.50-1.20 ml/g.
  5. 5. A method for preparing the catalyst according to claim 1, comprising impregnating an alumina carrier containing sulfate with a solution containing a palladium compound, a platinum compound and a chlorine compound, drying the impregnated solid, activating the solid at 400-650 ℃ in an air atmosphere, and reducing the solid at 350-550 ℃ with hydrogen, wherein the mass ratio of Pd/Pt in the solution is 2.2-6.0:1.
  6. 6. The process according to claim 5, wherein the sulfate-containing alumina support is prepared by shaping a sulfate-containing alumina precursor.
  7. 7. The method according to claim 5, wherein the sulfate-containing alumina carrier is prepared by preparing a shaped alumina carrier from pseudo-boehmite and introducing sulfate into the shaped alumina carrier.
  8. 8. The method according to claim 5, wherein the sulfate-containing alumina carrier is prepared by preparing a shaped alumina carrier from high-purity pseudo-boehmite, and introducing sulfate into the shaped alumina carrier.
  9. 9. The method according to claim 6 or 7, characterized in that the alumina carrier containing sulfate or the shaped alumina carrier is treated with water vapor at 400-700 ℃ for 0.5-120 hours, the mass ratio of water vapor to carrier being 0.2-10.
  10. 10. A method according to claim 6, 7 or 8, characterized in that the sulphate in the sulphate-containing alumina precursor or the sulphate introduced into the shaped alumina support is derived from sulphuric acid or sulphate.
  11. 11. The method of claim 10, wherein the sulfate is selected from the group consisting of aluminum sulfate, ammonium sulfate and aluminum ammonium sulfate.
  12. 12. The method of claim 5, wherein the palladium-containing compound is selected from the group consisting of palladium chloride, palladium nitrate, palladium acetate, sodium tetrachloropalladate, palladium dichlorotetraamine, palladium trifluoroacetate, palladium diacetylacetonate and palladium hexafluoroacetylacetonate.
  13. 13. The method of claim 5, wherein the platinum-containing compound is selected from the group consisting of chloroplatinic acid, tetraamineplatinum dichloride, ammonium chloroplatinate, platinum trichloride, platinum tetrachloride, platinum dicarbonyl dichloride, dinitrodiammine platinum, and sodium tetranitroplatinate.
  14. 14. The process according to claim 5, wherein the chlorine-containing compound is hydrochloric acid.
  15. 15. A method for selectively hydrodeolefinating reforming generated oil comprises the step of carrying out contact reaction on the reforming generated oil and the hydrodeolefinating catalyst in the claim 1 under the hydrogenation condition of 50-300 ℃, 0.5-5.0 MPa, volume space velocity of 2.0-30.0 h -1 and hydrogen/oil volume ratio of 2-500.
  16. 16. The method of claim 15, wherein the reformate is naphtha reformate or a benzene fraction, BTX fraction or reformate raffinate obtained from aromatic extraction of reformate.

Description

Hydrogenation olefin removal catalyst for reformate, preparation method and application Technical Field The invention relates to a hydrocarbon component selective hydrogenation olefin removal catalyst and a preparation method and application thereof, in particular to a reforming oil selective hydrogenation olefin removal catalyst and a preparation method and application thereof. Background Catalytic reforming is one of the mainstay technologies of modern petroleum refining and petrochemical industry. The method is a process of converting naphtha into reformed oil rich in aromatic hydrocarbon and producing hydrogen as byproduct by carrying out hydrocarbon molecular structure rearrangement reaction under the conditions of certain temperature, pressure, hydrogen and the presence of a catalyst. The reformed oil is rich in aromatic hydrocarbon and contains a small amount of olefin. The small amount of olefins present in the reformate may polymerize in the extraction solvent and contaminate the extraction solvent, while it may have varying degrees of impact on downstream equipment, adsorbents, and catalyst performance. In addition, the nature of olefins, particularly diolefins, is relatively reactive and can easily form gum and other byproducts that can easily contaminate the heat transfer surfaces of the operating equipment, thereby reducing its efficiency of use. As the severity of reforming, particularly continuous reformers, increases, the olefin content of the reformate also tends to increase significantly. Thus, removal of olefins from reformate is a challenge to be addressed in industry. The olefin in the reformed oil can be removed by clay adsorption, molecular sieve catalytic refining and selective hydrogenation, wherein the clay adsorption and the molecular sieve catalytic refining are non-hydrofining processes, and are limited to removing olefin in the reformed oil with bromine index below 1500mgBr/100g oil or mixed aromatic hydrocarbon. For removing olefin in the reformed oil with bromine index higher than 2000mgBr/100g oil, a hydrofining process is needed. The selective hydrogenation means that the olefin is removed by selective hydrogenation of the reformed oil and the raffinate oil under the condition of hydrogenation, and the deep hydrogenation is realized under the condition that the aromatic hydrocarbon is not saturated by hydrogenation. The catalyst mainly comprises non-noble metals (such as Co-Mo or Ni-Mo) and noble metals (containing Pt, pd and the like). The conventional sulfided non-noble metal Co-Mo or Ni-Mo hydrofining catalyst is adopted, and is operated at a higher reaction temperature (300-350 ℃) and a lower space velocity (2.0-3.0 h -1), so that the requirements of deep olefin removal (bromine index is less than 100mgBr/100g of oil) and aromatic hydrocarbon loss less than 0.5wt% in the hydrogenation process are difficult to achieve. In addition, because the reformed oil and the reformed hydrogen do not contain sulfur, the sulfur-free non-noble metal Co-Mo or Ni-Mo hydrofining catalyst is easy to lose sulfur to cause deactivation, and the sulfur precipitated during the regeneration of the Co-Mo or Ni-Mo hydrofining catalyst can seriously pollute the platinum-based catalyst in the reforming reactor. The catalyst containing noble metals Pt, pd and the like can deeply remove olefin in the reformed oil at a lower reaction temperature (100-250 ℃) and a higher space velocity (5.0-15.0 h -1), the bromine index of the product is small, and the aromatic hydrocarbon loss in the hydrogenation process is small. CN200710177193.8 discloses a hydrogenation catalyst for reforming generated oil and a preparation method thereof, and the catalyst comprises three parts of main active components, auxiliary agents and carriers. The main active component is a double noble metal component, pd is one of the main active components, the other main active component is one of Au, ag, pt, rh, ir, and the auxiliary agent is one of Sn, pb, sb, bi. Inorganic acid or organic acid is used as competitive adsorbent, and the pH value of the impregnating solution is regulated to 4-5 to make the double active components in the carrier be in eggshell type shallow layer distribution. CN200910056812.7 discloses a catalyst for removing olefins from reformate under hydrogen condition, which comprises 0.01-6.0 parts of a metal or oxide selected from Pt, pd, ru or Ni, 0.1-5.0 parts of a metal or oxide selected from K, mg, ca or Ba, 0.01-2.0 parts of a metal or oxide selected from lanthanide rare earth elements, and 90-100 parts of a carrier selected from at least one of SiO 2、Al2O3、TiO2 or ZnO. The catalyst can be used in the process of hydro-dealkening of reforming generated oil. Mainly solves the problems of low catalyst activity, short service life, large aromatic hydrocarbon loss, complex preparation process and large noble metal consumption in the prior art, but the catalyst is only suitable for removing olefin in reformed oil