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CN-121972162-A - Preparation method of Ru-Zn bimetallic catalyst loaded by carbon nano tube and used for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride

CN121972162ACN 121972162 ACN121972162 ACN 121972162ACN-121972162-A

Abstract

The invention relates to a preparation method of a Ru-Zn bimetallic catalyst loaded by a carbon nano tube for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, belonging to the technical field of catalysts. The preparation method comprises the steps of drying a carbon nano tube, immersing the carbon nano tube in RuCl3 solution, stirring, carrying out ultrasonic treatment, immersing the Ru-loaded carbon nano tube in zinc chloride solution, stirring, drying to obtain Ru/Zn intermediate, adding the Ru/Zn intermediate into sodium hydroxide solution, adding tetraallyl ammonium bromide and 2, 5-dimercaptothiadiazole disodium salt, heating, stirring for reaction, drying, placing a sample in an HCl atmosphere, and activating to obtain the nano Ru-Zn bimetallic catalyst.

Inventors

  • WANG LU
  • SHI YUYING
  • WANG FUMIN
  • CAI YINGHUI
  • LI JIEHAO
  • LI YONGWANG
  • ZHANG XUBIN
  • LIU QINGZHAO
  • REN HAILUN
  • CAO SHUAI

Assignees

  • 天津大学
  • 滨化集团股份有限公司

Dates

Publication Date
20260505
Application Date
20260319

Claims (10)

  1. 1. The preparation method of the carbon nano tube supported Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride comprises the following operation steps of: S1, soaking 50-100 parts of carbon nanotubes in 500-1000 parts of RuCl 3 solution after drying for 0.8-1.2 hours at 250-320 ℃, stirring for 25-35min at 25-35 ℃, carrying out ultrasonic treatment, drying, soaking the Ru-loaded carbon nanotubes in 500-1000 parts of zinc chloride solution, stirring, filtering, and drying to obtain an Ru/Zn intermediate; s2, adding 50-100 parts of Ru/Zn intermediate into 500-1000 parts of sodium hydroxide solution, adding 1-3 parts of tetraallyl ammonium bromide and 1.5-3.5 parts of 2, 5-dimercaptothiadiazole disodium salt, heating, stirring, reacting, drying, placing a sample in an HCl atmosphere, and activating to obtain the nanoscale Ru-Zn bimetallic catalyst.
  2. 2. The method for preparing the Ru-Zn supported bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the diameter of the carbon nano tube particles is 0.4-0.8 mm.
  3. 3. The method for preparing the Ru-Zn supported bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the RuCl 3 solution contains 0.2-0.4wt% Ru.
  4. 4. The method for preparing the carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the zinc chloride solution contains 2-4wt% Zn.
  5. 5. The preparation method of the carbon nano tube supported Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the ultrasonic temperature of S1 is 200-300 ℃ and the time is 0.8-1.2h.
  6. 6. The preparation method of the carbon nano tube supported Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the drying temperature of S1 is 250-320 ℃ and the time is 4-6h.
  7. 7. The method for preparing the carbon nano tube supported Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the mass percentage of the sodium hydroxide solution is 5-10%.
  8. 8. The preparation method of the carbon nano tube supported Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the temperature rise and stirring reaction temperature of S2 is 80-90 ℃ and the time is 20-60min.
  9. 9. The preparation method of the carbon nano tube supported Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, which is characterized by comprising 10-20% of the volume fraction of HCl of S2.
  10. 10. The preparation method of the carbon nano tube supported Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the activation temperature of S2 is 110-130 ℃ and the time is 20-65min.

Description

Preparation method of Ru-Zn bimetallic catalyst loaded by carbon nano tube and used for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride Technical Field The invention relates to the technical field of catalysts, in particular to a preparation method of a Ru-Zn bimetallic catalyst loaded by a carbon nano tube and used for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride. Background Electronic grade hydrogen chloride is used as an important electron special gas in the semiconductor manufacturing process, and the purity requirement is extremely high. Among these, trace amounts of acetylene and ethylene impurities can severely impact the quality and performance of semiconductor products. Chinese patent CN119524849A, belonging to the technical field of high purity gas preparation and catalysis, discloses a copper-iron double-component composite catalyst for removing trace acetylene and ethylene in petrochemical byproduct hydrogen chloride gas to prepare electronic grade hydrogen chloride gas, and the preparation method of the copper-iron double-component composite catalyst comprises the following steps of immersing carbon nanotubes in hydrochloric acid, washing the carbon nanotubes to pH neutrality by deionized water, and drying to obtain a pretreated carbon nanotube carrier; and (3) dipping the active component on the carbon nano tube carrier obtained by pretreatment, carrying out ultrasonic auxiliary dipping, standing and drying to obtain the active component, wherein the active component is Fe metal salt and Cu metal salt. At present, a plurality of methods for removing acetylene and ethylene impurities in electronic grade hydrogen chloride exist, but a plurality of problems exist. The traditional adsorption method has limited adsorption selectivity to impurities, and is difficult to realize deep removal, and the partial catalytic hydrogenation method can remove impurities, but the catalyst is easy to accumulate carbon and deactivate, and metal particles are easy to agglomerate in high-temperature reaction, so that the catalytic activity is reduced. Therefore, the development of a catalyst which is efficient, stable and can deeply remove trace acetylene and ethylene impurities in electronic grade hydrogen chloride has important practical significance. Disclosure of Invention In order to solve the problems, the invention provides a preparation method of a Ru-Zn bimetallic catalyst loaded on a carbon nano tube for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, which comprises the following operation steps in parts by mass: S1, soaking 50-100 parts of carbon nanotubes in 500-1000 parts of RuCl 3 solution after drying for 0.8-1.2 hours at 250-320 ℃, stirring for 25-35min at 25-35 ℃, carrying out ultrasonic treatment, drying, soaking the Ru-loaded carbon nanotubes in 500-1000 parts of zinc chloride solution, stirring, filtering, and drying to obtain an Ru/Zn intermediate; S2, adding 50-100 parts of Ru/Zn intermediate into 500-1000 parts of sodium hydroxide solution, adding 1-3 parts of tetraallyl ammonium bromide, wherein the CAS number is 19781-77-2, 1.5-3.5 parts of 2, 5-dimercaptothiadiazole disodium salt, the CAS number is 55906-42-8, heating and stirring for reaction, drying, and placing a sample in an HCl atmosphere for activation to obtain the nanoscale Ru-Zn bimetallic catalyst. Preferably, the diameter of the carbon nano tube particles is 0.4-0.8 mm. Preferably, the RuCl 3 solution contains 0.2-0.4wt% Ru. Preferably, the zinc chloride solution contains 2-4wt% Zn. Preferably, the ultrasonic temperature of S1 is 200-300 ℃ and the time is 0.8-1.2h. Preferably, the drying temperature of S1 is 250-320 ℃ and the time is 4-6h. Preferably, the mass percentage of the sodium hydroxide solution is 5-10%. Preferably, the temperature of the S2 is 80-90 ℃ and the time is 20-60min. Preferably, the HCl volume fraction of the S2 is 10-20%. Preferably, the activation temperature of S2 is 110-130 ℃ and the time is 20-65min. Reaction mechanism: Under the activation of HCl atmosphere, nanoscale Ru-Zn bimetal forms a synergistic catalytic active center, tetraallyl ammonium bromide and 2, 5-dimercaptothiadiazole disodium salt are used as a composite modifier, the electronic structure and dispersibility of the bimetal can be regulated, acetylene, ethylene and hydrogen chloride can be subjected to hydrochlorination on the active site of the catalyst, and the directional conversion of unsaturated hydrocarbon impurities is realized, so that the deep removal from the electronic grade hydrogen chloride is completed. The technical effects are as follows: The Ru-Zn bimetallic catalyst prepared has excellent catalytic removal performance on acetylene and ethylene impurities in electronic grade hydrogen chloride, can realize deep removal of two unsaturated hydrocarbon impurities, and meets the high-purity industry requirem