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CN-122006806-A - Preparation method of carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride

CN122006806ACN 122006806 ACN122006806 ACN 122006806ACN-122006806-A

Abstract

The invention relates to a preparation method of a carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, which comprises the steps of dissolving a polyoxypropylene polyoxyethylene copolymer in a methanol solution, adding cyclohexane, stirring to obtain a solution 1, heating and stirring chitosan, ethylenediamine and KOH to obtain a solution 2, dripping the solution 1 into the solution 2, heating and stirring for reaction, standing for precipitation, washing with ethanol, vacuum drying to obtain an amino carrier precursor, grinding the amino carrier precursor into a granular filler, vacuum drying, calcining at a high temperature in a nitrogen atmosphere, cooling a carbon nano tube to room temperature, and adding a modified supported boron-nitrogen catalyst resin.

Inventors

  • CAI YINGHUI
  • MA JIYUAN
  • WANG FUMIN
  • WANG LU
  • LI YONGWANG
  • JIN JICHAO
  • ZHANG XUBIN
  • SHEN WENHUI
  • LIU QINGZHAO
  • GUO JUANJUAN

Assignees

  • 天津大学
  • 滨化集团股份有限公司

Dates

Publication Date
20260512
Application Date
20260408

Claims (8)

  1. 1. A preparation method of a carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride comprises the following operation steps: H1, dissolving 30-50 parts of polyoxypropylene polyoxyethylene copolymer in 300-380 parts of methanol solution, adding 6-10 parts of cyclohexane, and stirring for 90-130min to obtain solution 1; Heating and stirring 18-22 parts of chitosan, 28-32 parts of ethylenediamine and 5-6 parts of 0.05M KOH to prepare solution 2; H3, slowly dripping the solution 1 into the solution 2, heating, stirring, reacting, standing, precipitating, washing with ethanol for 3-5 times, and vacuum drying to obtain an amino carrier precursor; grinding the amino carrier precursor into 80-120 mesh granular filler, vacuum drying, and calcining at high temperature in nitrogen atmosphere; H5, cooling the carbon nano tube to room temperature, adding 0.01-0.05 part of 2-dihydroxyboron-3-thiophenecarboxylic acid, 1-5 parts of ferric acetylacetonate and 1000-1200 parts of water, heating and stirring for reaction, then adjusting the pH to 4.5-5.5 by using a hydrochloric acid solution, filtering and drying to obtain the modified supported boron-nitrogen catalyst resin.
  2. 2. The preparation method of the carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, which is characterized in that the mass percentage of the H1 methanol solution is 20-35%.
  3. 3. The preparation method of the carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the reaction temperature of H2 is 80-100 ℃ and the time is 90-130min.
  4. 4. The preparation method of the carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the reaction temperature of H3 is 40-60 ℃ and the time is 90-130min.
  5. 5. The preparation method of the carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the drying temperature of H4 is 80-100 ℃ and the time is 2-3H.
  6. 6. The preparation method of the carbon nano tube supported boron nitrogen catalyst for deeply removing trace amounts of acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the high-temperature calcination temperature of H4 is 350-390 ℃ and the time is 1.5-2.5H.
  7. 7. The preparation method of the carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride according to claim 1, wherein the reaction temperature of H5 is 70-90 ℃ and the time is 100-140min.
  8. 8. The preparation method of the carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, which is characterized in that the mass percentage of the hydrochloric acid solution of H5 is 9-13%.

Description

Preparation method of carbon nano tube supported boron-nitrogen catalyst for deeply 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 carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride. Background In the electronic industry, electronic grade hydrogen chloride is used as a key electronic chemical, and has a critical influence on the performance, the integration level and the yield of electronic products such as chips. Currently, the united states is the major exporting country for electronic grade hydrogen chloride, which often uses petrochemical by-product hydrogen chloride as a preparation raw material. The petrochemical byproduct hydrogen chloride gas has the advantage of low water content, so that the petrochemical byproduct hydrogen chloride gas is basically corrosion-free to stainless steel and carbon steel, is relatively simple to operate and has low production cost. However, acetylene and ethylene impurities are present in the feedstock, and their removal becomes a technical difficulty in the preparation of electronic grade hydrogen chloride. Chinese patent CN114634163B discloses a production device and a production method for producing electronic grade hydrogen chloride, wherein the device comprises an adsorption tower, a cooler, a raw material rectifying tower, a first heavy removal tower, a flash tank, a reactor, a light removal tower, a motor tower, a second heavy removal tower and a membrane separation device, wherein an ejection port of the adsorption tower is connected with a tower bottom feed port of the raw material rectifying tower through the cooler, the tower bottom feed port of the first heavy removal tower is connected with the tower bottom of the raw material rectifying tower, an inlet of the flash tank is connected with the tower top of the first heavy removal tower, the bottom of the reactor is connected with the top of the flash tank, the tower bottom of the motor tower is connected with the bottom of the light removal tower, the second heavy removal tower is connected with the tower top of the motor tower or the tower bottom of the motor tower, and the membrane separation device is connected with the tower top of the second heavy removal tower. The Chinese patent CN119349509A discloses a method for preparing electronic grade hydrogen chloride in a semi-continuous way in the field of electronic gas preparation, which comprises the following steps of (1) utilizing a cryogenic system to enable the moisture content of industrial hydrogen chloride to be lower than 50ppm, then introducing the industrial hydrogen chloride into an adsorption system, (2) utilizing the adsorption system to deeply remove trace moisture in the hydrogen chloride, after the moisture content of the hydrogen chloride is lower than 1ppm, introducing the industrial hydrogen chloride into a filtering system, (3) utilizing the filtering system to remove powdered adsorbent carried by anhydrous hydrogen chloride gas, then introducing the anhydrous hydrogen chloride into a rectifying tower feed tank, (4) introducing the anhydrous hydrogen chloride in the rectifying tower feed tank into a heavy component removal tower, removing high-boiling-point impurities from the tower bottom, introducing materials at the tower top into the light component removal tower, and (5) continuously evacuating the tower top of the light component removal tower to remove the light-boiling-point impurities, and opening a collecting valve when the purity of the hydrogen chloride in the tower bottom material is more than 99.9995%, and filling. The prior art cannot efficiently remove acetylene and methane impurities, and the purity of the product is still to be further improved. Disclosure of Invention In order to solve the problems, the invention provides a preparation method of a carbon nano tube supported boron-nitrogen catalyst for deeply removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, which comprises the following operation steps: h1, dissolving 30-50 parts of polyoxypropylene polyoxyethylene copolymer in 300-380 parts of methanol solution, dissolving polyoxypropylene polyoxyethylene copolymer in 100-180 parts of methanol solution, adding 6-10 parts of cyclohexane, and stirring for 90-130min to obtain solution 1; Heating and stirring 18-22 parts of chitosan, 28-32 parts of ethylenediamine and 5-6 parts of 0.05M KOH to prepare solution 2; H3, slowly dripping the solution 1 into the solution 2, heating, stirring, reacting, standing, precipitating, washing with ethanol for 3-5 times, and vacuum drying to obtain an amino carrier precursor; grinding the amino carrier precursor into 80-120 mesh granular filler, vacuum drying, and calcining at high temperature in