Preparation method of carbon nanotube loaded Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride

Abstract

The invention relates to a preparation method of a carbon nanotube loaded Ru-Zn bimetallic catalyst for removing trace acetylene and ethylene impurities in electronic grade hydrogen chloride, and belongs to the technical field of catalysts. The method comprises the following steps: drying a carbon nanotube, dipping the carbon nanotube in a RuCl solution, stirring, carrying out ultrasonic treatment, and drying; dipping the Ru-loaded carbon nanotube in a zinc chloride solution, stirring, and drying to obtain a Ru / Zn intermediate; adding the Ru / Zn intermediate into a sodium hydroxide solution, adding tetraallylammonium bromide and 2, 5-dimercaptothiadiazole disodium salt, heating and stirring for reaction, and drying; placing the sample in an HCl atmosphere, and activating to obtain a nanoscale Ru-Zn bimetallic catalyst; the prepared catalyst has extremely high catalytic activity on trace acetylene and ethylene impurities in electronic-grade hydrogen chloride, can deeply remove the impurities, and meets the requirement of the electronic-grade hydrogen chloride on high purity.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride. Background Technology

[0002] Electronic-grade hydrogen chloride is an important electronic specialty gas in semiconductor manufacturing, and its purity requirements are extremely high. Even trace amounts of acetylene and ethylene impurities can severely affect the quality and performance of semiconductor products.

[0003] Chinese Patent CN119524849A: Belonging to the field of high-purity gas preparation and catalysis technology, it discloses a copper-iron bicomponent composite catalyst for removing trace amounts of acetylene and ethylene from petrochemical byproduct hydrogen chloride gas to prepare electronic-grade hydrogen chloride gas. The preparation method of the copper-iron bicomponent composite catalyst includes the following steps: immersing carbon nanotubes in hydrochloric acid, washing them with deionized water until the pH is neutral, and drying them to obtain a pretreated carbon nanotube support; impregnating the active components onto the pretreated carbon nanotube support using ultrasonic-assisted impregnation, allowing it to stand, and then drying it to obtain the final product; the active components are Fe metal salt and Cu metal salt.

[0004] Currently, numerous methods exist for removing acetylene and ethylene impurities from electronic-grade hydrogen chloride, but these methods suffer from several problems. Traditional adsorption methods have limited selectivity for impurities, making deep removal difficult. While some catalytic hydrogenation methods can remove impurities, the catalysts are prone to carbon deposition and deactivation, and metal particles tend to agglomerate during high-temperature reactions, leading to a decrease in catalytic activity. Therefore, developing a highly efficient, stable catalyst capable of deeply removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride is of significant practical importance. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride. The operational steps are as follows, in parts by mass: S1: After drying 50-100 parts of carbon nanotubes at 250-320℃ for 0.8-1.2h, they are immersed in 500-1000 parts of RuCl3 solution, stirred at 25-35℃ for 25-35min, sonicated, and dried; the Ru-loaded carbon nanotubes are immersed in 500-1000 parts of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate; S2: Add 50-100 parts of Ru / Zn intermediate to 500-1000 parts of sodium hydroxide solution, add 1-3 parts of tetraallylammonium bromide (CAS No.: 19781-77-2) and 1.5-3.5 parts of 2,5-dimercaptothiadiazole disodium salt (CAS No.: 55906-42-8); after heating and stirring the reaction, dry the sample; place the sample in an HCl atmosphere to activate it, and obtain nanoscale Ru-Zn bimetallic catalyst.

[0006] Preferably, the carbon nanotube particles have a diameter of 0.4-0.8 mm.

[0007] Preferably, the RuCl3 solution contains 0.2-0.4 wt% Ru.

[0008] Preferably, the zinc chloride solution contains 2-4 wt% Zn.

[0009] Preferably, the ultrasonic temperature of S1 is 200-300℃ and the time is 0.8-1.2h.

[0010] Preferably, the drying temperature of S1 is 250-320℃ and the drying time is 4-6 hours.

[0011] Preferably, the sodium hydroxide solution has a mass percentage of 5-10%.

[0012] Preferably, the heating and stirring reaction temperature of S2 is 80-90℃, and the time is 20-60 min.

[0013] Preferably, the HCl volume fraction of S2 is 10-20%.

[0014] Preferably, the activation temperature of S2 is 110-130℃ and the activation time is 20-65 min.

[0015] Reaction mechanism: Under the activation effect of HCl atmosphere, nano-sized Ru-Zn bimetals form synergistic catalytic active centers. Tetraallylammonium bromide and 2,5-dimercaptothiadiazole disodium salt serve as composite modifiers, which can regulate the electronic structure and dispersion of the bimetals, enabling acetylene, ethylene, and hydrogen chloride to undergo hydrochlorination reactions at the catalyst active sites, achieving the directional conversion of unsaturated hydrocarbon impurities, thereby completing the deep removal from electronic-grade hydrogen chloride.

[0016] Technical effects: The prepared Ru-Zn bimetallic catalyst exhibits excellent catalytic removal performance for acetylene and ethylene impurities in electronic-grade hydrogen chloride, enabling deep removal of these two types of unsaturated hydrocarbon impurities and meeting the industry requirements for high purity of electronic-grade hydrogen chloride.

[0017] During catalyst preparation, the dispersion and stability of the bimetallic active center were improved by regulating the composite modifier and using a stepwise loading activation process, which effectively avoided the problem of metal particle agglomeration and ensured the long-term catalytic performance.

[0018] The catalyst has a controllable and mild preparation process. It achieves efficient loading of active components by relying on the characteristics of carbon nanotube support. The catalytic reaction process is compatible with the purification process of electronic-grade hydrogen chloride, making it highly applicable. Attached Figure Description

[0019] Figure 1 Diagram of an acetylene / ethylene hydrochlorination reactor; Figure 2 The conversion rate of the Ru-Zn / AC bimetallic catalyst in the hydrochlorination of acetylene / ethylene; Figure 3 The conversion rate of Ru / AC in the hydrochlorination of acetylene / ethylene; Figure 4 Transmission electron microscopy image of a fresh Ru-Zn catalyst; Figure 5 This is a scanning electron microscope image of a fresh Ru-Zn catalyst. Detailed Implementation

[0020] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with the accompanying drawings and preferred embodiments, is provided below.

[0021] The C2H2 / C2H4 / N2 mixture (C2H2 and C2H4 content are both 5000ppm), HCl (99.99%) and N2 (99.99%) were purchased from Tianjin Dongxiang Special Gases Co., Ltd., and all other reagents were purchased from Aladdin Biochemical Technology Co., Ltd.

[0022] Catalyst drying: The catalyst is loaded into the reaction tube, the temperature of the Tianjin Zhongke FX-50 fixed bed reactor heater is raised to 120℃, and nitrogen is continuously introduced for 30 minutes; Catalyst activation: Replace nitrogen with HCl and raise the furnace temperature to 250℃ for 30 min; Reaction and gas treatment: After activation, C2H2 / C2H4 / N2 and HCl are introduced and reacted for 40 hours; the gas after reaction is passed into sodium hydroxide solution to remove the remaining HCl; then the gas is passed through anhydrous calcium chloride to absorb the moisture in the gas. Gas chromatography analysis: The treated gas is passed into a gas chromatograph (SP-3420A) for analysis to determine the content of acetylene and ethylene in the gas after the reaction, and to calculate the removal rate of acetylene and ethylene by the catalyst. Example 1

[0023] A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps: S1: After drying 50g of carbon nanotubes at 250℃ for 0.8h, they were immersed in 500g of RuCl3 solution, stirred at 25℃ for 25min, sonicated, and dried; the Ru-loaded carbon nanotubes were immersed in 500g of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate. S2: Add 50g of Ru / Zn intermediate to 500g of sodium hydroxide solution, add 1g of tetraallylammonium bromide (CAS No.: 3571-74-2) and 1.5g of 2,5-dimercaptothiadiazole disodium salt, heat and stir the reaction, and then dry; place the sample in an HCl atmosphere to activate it, and obtain nanoscale Ru-Zn bimetallic catalyst.

[0024] The carbon nanotube particles have a diameter of 0.4 mm.

[0025] The RuCl3 solution contains 0.2 wt% Ru.

[0026] The zinc chloride solution contains 2 wt% Zn.

[0027] The ultrasonic temperature of S1 is 200℃ and the time is 0.8h.

[0028] The drying temperature of S1 is 250℃ and the drying time is 4 hours.

[0029] The sodium hydroxide solution has a mass percentage of 5%.

[0030] The reaction temperature of S2 is 80℃ and the reaction time is 20 min.

[0031] The volume fraction of HCl in S2 is 10%.

[0032] The activation temperature of S2 is 110℃ and the activation time is 20 min. Example 2

[0033] A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps: S1: 62g of carbon nanotubes were dried at 270℃ for 0.9h, then immersed in 600g of RuCl3 solution, stirred at 28℃ for 30min, sonicated, and dried; the Ru-loaded carbon nanotubes were immersed in 600g of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate. S2: Add 60g of Ru / Zn intermediate to 700g of sodium hydroxide solution, add 2g of tetraallylammonium bromide (CAS No.: 3571-74-2) and 2g of 2,5-dimercaptothiadiazole disodium salt, heat and stir the reaction, and then dry; place the sample in an HCl atmosphere to activate it, and obtain nanoscale Ru-Zn bimetallic catalyst.

[0034] The carbon nanotube particles have a diameter of 0.5 mm.

[0035] The RuCl3 solution contains 0.3 wt% Ru.

[0036] The zinc chloride solution contains 3 wt% Zn.

[0037] The ultrasonic temperature of S1 is 240℃, and the time is 0.9h.

[0038] The drying temperature of S1 is 270℃ and the drying time is 5 hours.

[0039] The sodium hydroxide solution has a mass percentage of 6%.

[0040] The reaction temperature of S2 is 85℃ and the reaction time is 30 min.

[0041] The volume fraction of HCl in S2 is 15%.

[0042] The activation temperature of S2 is 115℃ and the activation time is 35 min. Example 3

[0043] A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps: S1: After drying 80g of carbon nanotubes at 300℃ for 1.1h, they were immersed in 700g of RuCl3 solution, stirred at 33℃ for 30min, sonicated, and dried; the Ru-loaded carbon nanotubes were immersed in 700g of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate. S2: Add 90g of Ru / Zn intermediate to 900g of sodium hydroxide solution, add 2g of tetraallylammonium bromide (CAS No.: 3571-74-2) and 3g of 2,5-dimercaptothiadiazole disodium salt, heat and stir the reaction, and then dry; place the sample in an HCl atmosphere to activate it, and obtain nanoscale Ru-Zn bimetallic catalyst.

[0044] The carbon nanotube particles have a diameter of 0.7 mm.

[0045] The RuCl3 solution contains 0.3 wt% Ru.

[0046] The zinc chloride solution contains 3 wt% Zn.

[0047] The ultrasonic temperature of S1 is 280℃, and the time is 1.1h.

[0048] The drying temperature of S1 is 300℃ and the drying time is 5 hours.

[0049] The sodium hydroxide solution has a mass percentage of 8%.

[0050] The reaction temperature of S2 is 85℃ and the reaction time is 50 min.

[0051] The volume fraction of HCl in S2 is 15%.

[0052] The activation temperature of S2 is 125℃ and the activation time is 55 min. Example 4

[0053] A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps: S1: After drying 100g of carbon nanotubes at 320℃ for 1.2h, they were immersed in 1000g of RuCl3 solution, stirred at 35℃ for 35min, sonicated, and dried; the Ru-loaded carbon nanotubes were immersed in 1000g of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate. S2: 100g of Ru / Zn intermediate was added to 1000g of sodium hydroxide solution, along with 3g of tetraallylammonium bromide (CAS No.: 3571-74-2) and 3.5g of 2,5-dimercaptothiadiazole disodium salt. After heating and stirring, the mixture was dried. The sample was then placed in an HCl atmosphere for activation to obtain a nanoscale Ru-Zn bimetallic catalyst.

[0054] The carbon nanotube particles have a diameter of 0.8 mm.

[0055] The RuCl3 solution contains 0.4 wt% Ru.

[0056] The zinc chloride solution contains 3 wt% Zn.

[0057] The ultrasonic temperature of S1 is 300℃, and the time is 1.2h.

[0058] The drying temperature of S1 is 320℃ and the drying time is 6 hours.

[0059] The sodium hydroxide solution has a mass percentage of 10%.

[0060] The reaction temperature of S2 is 90℃ and the reaction time is 60 min.

[0061] The volume fraction of HCl in S2 is 20%.

[0062] The activation temperature of S2 is 130℃ and the activation time is 65 min.

[0063] Comparative Example 1 A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps: S1: After drying 50g of carbon nanotubes at 250℃ for 0.8h, they were immersed in 500g of RuCl3 solution, stirred at 25℃ for 25min, sonicated, and dried; the Ru-loaded carbon nanotubes were immersed in 500g of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate. The carbon nanotube particles have a diameter of 0.4 mm.

[0064] The RuCl3 solution contains 0.2 wt% Ru.

[0065] The zinc chloride solution contains 2 wt% Zn.

[0066] The ultrasonic temperature was 200℃ and the time was 0.8h.

[0067] The drying temperature is 250℃ and the time is 4 hours.

[0068] Comparative Example 2 A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps: S1: After drying 50g of carbon nanotubes at 250℃ for 0.8h, they were immersed in 500g of RuCl3 solution, stirred at 25℃ for 25min, sonicated, and dried; the Ru-loaded carbon nanotubes were immersed in 500g of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate. S2: Add 50g of Ru / Zn intermediate to 500g of sodium hydroxide solution, add 1.5g of 2,5-dimercaptothiadiazole disodium salt, heat and stir the reaction, and then dry; place the sample in an HCl atmosphere to activate it, and obtain nanoscale Ru-Zn bimetallic catalyst.

[0069] The carbon nanotube particles have a diameter of 0.4 mm.

[0070] The RuCl3 solution contains 0.2 wt% Ru.

[0071] The zinc chloride solution contains 2 wt% Zn.

[0072] The ultrasonic temperature of S1 is 200℃ and the time is 0.8h.

[0073] The drying temperature of S1 is 250℃ and the drying time is 4 hours.

[0074] The sodium hydroxide solution has a mass percentage of 5%.

[0075] The reaction temperature of S2 is 80℃ and the reaction time is 20 min.

[0076] The volume fraction of HCl in S2 is 10%.

[0077] The activation temperature of S2 is 110℃ and the activation time is 20 min.

[0078] Comparative Example 3 A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps: S1: After drying 50g of carbon nanotubes at 250℃ for 0.8h, they were immersed in 500g of RuCl3 solution, stirred at 25℃ for 25min, sonicated, and dried; the Ru-loaded carbon nanotubes were immersed in 500g of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate. S2: Add 50g of Ru / Zn intermediate to 500g of sodium hydroxide solution, add 1g of tetraallylammonium bromide (CAS No.: 3571-74-2), heat and stir to react, then dry; place the sample in an HCl atmosphere to activate it, and obtain nanoscale Ru-Zn bimetallic catalyst.

[0079] The carbon nanotube particles have a diameter of 0.4 mm.

[0080] The RuCl3 solution contains 0.2 wt% Ru.

[0081] The zinc chloride solution contains 2 wt% Zn.

[0082] The ultrasonic temperature of S1 is 200℃ and the time is 0.8h.

[0083] The drying temperature of S1 is 250℃ and the drying time is 4 hours.

[0084] The sodium hydroxide solution has a mass percentage of 5%.

[0085] The reaction temperature of S2 is 80℃ and the reaction time is 20 min.

[0086] The volume fraction of HCl in S2 is 10%.

[0087] The activation temperature of S2 is 110℃ and the activation time is 20 min.

[0088] The initial acetylene content was 5000 ppm, and the initial ethylene content was 5000 ppm.

[0089] Table 1: Test Results of Examples and Comparative Examples Acetylene removal rate (%) Ethylene removal rate (%) Example 1 99.38 99.19 Example 2 99.53 99.23 Example 3 99.81 99.30 Example 4 99.95 99.64 Comparative Example 1 83.56 84.98 Comparative Example 2 94.65 94.37 Comparative Example 3 97.72 96.21 The Ru-Zn bimetallic catalyst prepared in this invention exhibits extremely high removal efficiency for acetylene and ethylene impurities in electronic-grade hydrogen chloride, which is far superior to the control sample that has not been modified with sodium hydroxide system and without the addition of composite modifier, demonstrating the significant improvement effect of stepwise modification and activation process on catalytic performance.

[0090] Comparative Example 1, which did not undergo subsequent alkaline reaction and HCl atmosphere activation treatment, showed a significant decrease in impurity removal efficiency, indicating that the reaction process in the alkaline system and HCl activation are key steps in the formation of highly efficient nanoscale bimetallic catalytic centers, and neither can be omitted.

[0091] Comparative Examples 2 and 3, which were modified by removing one of the novel monomers, tetraallylammonium bromide and 2,5-dimercaptothiadiazole disodium salt, respectively, showed a significant decrease in impurity removal efficiency. This confirms that the two novel monomers form a synergistic effect in the catalytic system, which can effectively regulate the performance of the active site of the catalyst. This is an important innovation of this invention to achieve high removal efficiency. Only by adding both of them together can the catalyst fully exert its optimal catalytic effect.

[0092] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, comprising the following steps, in parts by mass: S1: After drying 50-100 parts of carbon nanotubes at 250-320℃ for 0.8-1.2h, they are immersed in 500-1000 parts of RuCl3 solution, stirred at 25-35℃ for 25-35min, sonicated, and dried; the Ru-loaded carbon nanotubes are immersed in 500-1000 parts of zinc chloride solution, stirred, filtered, and dried to obtain the Ru / Zn intermediate; S2: Add 50-100 parts of Ru / Zn intermediate to 500-1000 parts of sodium hydroxide solution, add 1-3 parts of tetraallylammonium bromide and 1.5-3.5 parts of 2,5-dimercaptothiadiazole disodium salt, heat and stir the reaction, and then dry; place the sample in an HCl atmosphere to activate it, and obtain nanoscale Ru-Zn bimetallic catalyst.

2. The method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride according to claim 1, characterized in that: The carbon nanotube particles have a diameter of 0.4-0.8 mm.

3. The method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride according to claim 1, characterized in that: The RuCl3 solution contains 0.2-0.4 wt% Ru.

4. The method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride according to claim 1, characterized in that: The zinc chloride solution contains 2-4 wt% Zn.

5. The method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride according to claim 1, characterized in that: The ultrasonic temperature of S1 is 200-300℃, and the time is 0.8-1.2h.

6. The method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride according to claim 1, characterized in that: The drying temperature of S1 is 250-320℃, and the drying time is 4-6 hours.

7. The method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride according to claim 1, characterized in that: The sodium hydroxide solution has a mass percentage of 5-10%.

8. The method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride according to claim 1, characterized in that: The temperature of the stirring reaction in S2 is 80-90℃, and the time is 20-60 min.

9. A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, as described in claim 1, characterized in that: The volume fraction of HCl in S2 is 10-20%.

10. A method for preparing a carbon nanotube-supported Ru-Zn bimetallic catalyst for removing trace amounts of acetylene and ethylene impurities from electronic-grade hydrogen chloride, as described in claim 1, characterized in that: The activation temperature of S2 is 110-130℃, and the activation time is 20-65 min.

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