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WO2024240099A1 - Catalyseur à base de ruthénium à dispersité élevée d'oxydation du chlorure d'hydrogène pour préparer du chlore et son procédé de préparation - Google Patents

Catalyseur à base de ruthénium à dispersité élevée d'oxydation du chlorure d'hydrogène pour préparer du chlore et son procédé de préparation Download PDF

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Publication number
WO2024240099A1
WO2024240099A1 PCT/CN2024/094092 CN2024094092W WO2024240099A1 WO 2024240099 A1 WO2024240099 A1 WO 2024240099A1 CN 2024094092 W CN2024094092 W CN 2024094092W WO 2024240099 A1 WO2024240099 A1 WO 2024240099A1
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ruthenium
catalyst
hydrogen chloride
preparing
carrier
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Chinese (zh)
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王定军
宋薛
李洪花
卢奇佳
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Canan Technique Material Hangzhou Inc
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Canan Technique Material Hangzhou Inc
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Priority claimed from CN202310575342.5A external-priority patent/CN116899558B/zh
Priority claimed from CN202310574910.XA external-priority patent/CN116550321A/zh
Application filed by Canan Technique Material Hangzhou Inc filed Critical Canan Technique Material Hangzhou Inc
Publication of WO2024240099A1 publication Critical patent/WO2024240099A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium

Definitions

  • the present application relates to the field of catalysts, and in particular to a high-dispersion ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation and a preparation method thereof.
  • Chlorine is an important basic chemical raw material, widely used in chemical, metallurgical, papermaking, textile, petrochemical, drinking water disinfection and environmental protection industries.
  • organochlorine products When producing organochlorine products in industry, a large amount of by-product hydrogen chloride is produced, with the maximum atomic utilization rate of 50%.
  • Most of these hydrogen chloride gases are absorbed by water to make hydrochloric acid, but they contain organic impurities, which limits their use.
  • the requirements for the transportation management and discharge of toxic and highly corrosive substances such as chlorine and hydrogen chloride are becoming more and more stringent, and the by-product hydrogen chloride is becoming more and more difficult to handle. Converting hydrogen chloride to prepare chlorine can realize the closed-loop recycling of chlorine resources. It is the most effective method for processing and recovering by-product hydrogen chloride, and a high degree of consensus has been formed in the chlorine-related industry.
  • Catalytic oxidation is the most effective solution, especially the catalytic oxidation via the Deacon reaction, which has the greatest potential for industrialization due to its simple operation and low equipment cost.
  • hydrogen chloride is oxidized to chlorine by oxygen exothermic equilibrium.
  • the conversion of hydrogen chloride to chlorine allows the production of chlorine to be separated from the production of sodium hydroxide by chlor-alkali electrolysis. The separation is very attractive because the world demand for chlorine is higher than that for sodium hydroxide.
  • Deacon catalyst copper-based catalyst
  • transition metal catalysts such as iron and chromium
  • highly active ruthenium-based (Ru), cerium-based (Ce) and composite oxide catalysts have been developed.
  • Copper-based catalysts have attracted much attention due to their low cost.
  • the name "an oxychlorination catalyst and its application” uses copper and oxide inert carriers, but as the reaction time at high temperature passes, copper particles will gather, and bridges will be formed between particles, causing the catalyst specific surface area to drop significantly, so that the activity decreases, thereby causing deactivation.
  • Copper-containing hydrogen chloride oxidation catalysts can be loaded with carriers that are inert to the hydrogen chloride oxidation reaction system, such as U.S. patent application US4123389A using silica gel, aluminum oxide or titanium oxide as carriers, copper is the main active component, but the preparation process requires organic solvent impregnation, which is environmentally polluting.
  • chromium catalysts Although chromium catalysts have good activity, chromium is highly toxic and its large-scale use has adverse effects on the environment.
  • U.S. Patent No. 5716592A reports the use of a composite catalyst of chromium oxide and rare earth cerium, with a loading of 45 g of catalyst, an HCl flow rate of 0.3 L/min, and an O 2 flow rate of 0.225 L/min, to catalytically oxidize hydrogen chloride at 380°C, with a conversion rate of up to 85.2%.
  • Chromium is toxic and easily forms low-boiling chromium oxychloride with chlorine, which easily deactivates the catalyst.
  • ruthenium catalyst for hydrogen chloride oxidation catalysis technology CN1182717A, CN1150127C and CN1272238C disclose the preparation of ruthenium-based catalysts by impregnating ruthenium oxide and calcining oxides such as TiO2 and ZrO2 as carriers.
  • WO2007/134772A1 of Bayer Materialscience AG discloses a ruthenium-based catalyst system containing tin dioxide.
  • ruthenium-based catalysts have the characteristics of low dosage and high low-temperature activity, for example, the ruthenium-based catalyst prepared by loading RuO2 and SiO2 on TiO2 in CN1182717A has better low-temperature catalytic performance.
  • the active component RuO2 particles are prone to sintering due to insufficient heat dissipation. After long-term use, the catalyst still has the problem of decreased reaction activity.
  • CN1272238C of Sumitomo Chemical discloses that a RuO2 catalyst supported on a composite carrier of rutile TiO2 and ⁇ -alumina reduces the reaction temperature of the Deacon process to about 300°C, and increases the theoretical equilibrium conversion rate to 90%-95%.
  • Ruthenium-based catalysts have two main advantages over other non-precious metal catalysts: first, they have good low-temperature activity at 300-350°C and high HCl equilibrium conversion rate; second, the chlorination of their surface active phase is self-limiting, and the catalyst will not generate volatile chlorides due to excessive chlorination.
  • ruthenium has poor high temperature resistance and is easily deactivated at high temperatures of 360-390°C, especially when the temperature is higher than 400°C.
  • researchers in this field are committed to improving ruthenium-based catalysts by further improving their activity and high-temperature thermal stability and reducing costs to achieve wider commercialization.
  • Sumitomo Chemical's CN101223104A uses rutile titanium dioxide and ⁇ -alumina mixed in different proportions as carriers to prepare a supported RuO 2 catalyst. The activity of this catalyst decreases continuously during the hydrogen chloride oxidation process, and the reaction temperature needs to be gradually increased to increase the hydrogen chloride conversion rate. At the same time, the activity decreases at high temperatures.
  • the Deacon reaction temperature is generally between 280-420°C, which is in a relatively high thermal environment.
  • the catalyst needs to have not only good thermal conductivity and thermal stability, but also a low specific surface area, such as 10-50m2 /g. Due to the thermal effect of the material, the material with a large specific surface area will decrease in specific surface area as the grain grows at high temperature and the pore structure changes. This is very unfavorable for the catalyst after loading the active component, which will cause the activity to decrease and accelerate deactivation.
  • the grain size and dispersion of the active components of the catalyst greatly affect the activity of the reaction.
  • high specific surface area materials are selected as carriers, which is conducive to the loading of active metals and higher dispersion. Due to the limitations of reaction conditions, the Deacon reaction requires a carrier with good thermal stability.
  • the purpose of the present application is to provide a catalyst for the oxidation of hydrogen chloride to produce chlorine, wherein the active component ruthenium is in a highly dispersed state; and to provide a ruthenium catalyst with a high carrier thermal conductivity; and a method for preparing the catalyst and using the catalyst to catalytically oxidize hydrogen chloride to chlorine by oxygen.
  • a method for preparing a highly dispersed ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation of the present application comprises the following steps:
  • the surfactant is selected from any one or more combinations of hydrophilic nonionic surfactants including but not limited to polyoxyethylene nonionic surfactants, polyethylene glycol, polysorbate, etc. More specifically, the surfactant is selected from any one or more combinations of T-80 (Tween-80), OP-10 (alkylphenol polyoxyethylene ether), PEG-400 (polyethylene glycol 400); T-80 is more preferably used as the surfactant.
  • the amount of the surfactant used is 1-10 times the mass of the metal element in the ruthenium active component, and more preferably 1-5 times.
  • the ruthenium active component described in the present application is derived from but not limited to any one or more combinations of the following components: RuCl 3 , RuCl 3 ⁇ xH 2 O, RuBr 3 , RuBr 3 ⁇ xH 2 O; chlororuthenates, such as K 3 RuCl 6 , (RuCl 3 ) 3- , K 2 RuCl 6 ; chlororuthenate hydrates, such as [RuCl 5 (H 2 O) 4 ] 2- , [RuCl 2 (H 2 O) 4 ] + ; ruthenates, such as K 2 RuO 4 or Na 2 RuO 4 ; ruthenium oxychloride, such as Ru 2 OCl 4 , Ru 2 OCl 5 , Ru 2 OCl 6 ; ruthenium oxychloride salts, such as K 2 Ru 2 OCl 10 , Cs 2 Ru 2 OCl 4 ; ruthenium ammine complexes, such as [Ru(NH 3 ) 6 ]
  • the active precious metal component ruthenium element accounts for 0.1-10wt% of the ruthenium catalyst, more preferably 0.5-5wt%, and most preferably 1-3wt%. A lower content of the active component will result in insufficient catalyst activity, while a higher content will increase the catalyst cost.
  • the impregnation method in step (2) is any one of equal volume impregnation, excess impregnation and spray impregnation.
  • the titanium oxide is preferably rutile titanium dioxide.
  • the aluminum oxide is selected as ⁇ -Al 2 O 3 and has a thermal conductivity of not less than 23W/m ⁇ °C.
  • the carrier prepared after molding has high thermal conductivity and more macropores, thereby improving the dissipation of heat generated during the reaction process, preventing the growth of ruthenium active component grains due to excessively high reaction temperature and the formation of agglomerates, and at the same time, it is also conducive to achieving a high dispersion state of ruthenium active components.
  • the composite carrier provided in the present application has significantly improved adsorption of metallic ruthenium under the pretreatment of the above-mentioned surfactant.
  • the composite carrier is prepared by a molding process, and its shape includes any one or more combinations of powder, spherical, columnar, special-shaped, and honeycomb.
  • the catalyst prepared after carrier impregnation and molding has a specific surface area of 10-50m2 /g, ruthenium grains of 1-10nm, and a ruthenium metal surface area of 120-410m2 /(g ⁇ Ru), which is highly dispersed.
  • the preparation process enhances thermal stability, which is conducive to extending service life and meeting the requirements of industrial catalysis and production.
  • the present application improves the preparation process and prepares a catalyst with higher ruthenium dispersion than existing catalysts on a carrier with a lower specific surface area.
  • the currently industrialized 1.5% Ru content catalyst has a surface area of about 130-200m2 /(g ⁇ Ru), while the surface area of the catalyst prepared by the present application method with the same 1.5% Ru content can reach 200-340m2 /(g ⁇ Ru).
  • the high dispersion increases the effective utilization rate of ruthenium atoms, greatly improves the catalyst activity, and can achieve higher activity under the condition of lower metal loading.
  • the present application loads the ruthenium active component after the carrier forming process, and the calcination after loading does not cause obvious sintering, which can effectively prevent the growth of metal grains, thereby preparing a catalyst with high dispersion.
  • the carrier material selected in the present application has the characteristics of acid and alkali resistance and stable high temperature performance.
  • the selection of high thermal conductivity materials is conducive to the timely removal of reaction heat, and the appropriate specific surface area is conducive to the dispersion of active metals.
  • the ruthenium catalyst provided in the present application is used for the preparation of chlorine by hydrogen chloride oxidation, and has good catalytic activity and high catalytic activity at low temperatures.
  • the ruthenium active component is added by a surfactant to form an impregnation solution, which is conducive to improving the adsorption of active metals by the carrier and improving the dispersion of metallic ruthenium.
  • High dispersion means that the effective utilization rate of metal atoms is increased, with high activity, while maintaining a high conversion rate, reducing the metal content, which is conducive to reducing the cost of the catalyst.
  • the present application provides a ruthenium catalyst, comprising a porous carrier and a Ruthenium active component; the porous carrier is derived from titanium oxide, high thermal conductivity ceramics and additive mixture, and the high thermal conductivity ceramics are selected from any one or more combinations of Si 3 N 4 , BN and SiC.
  • the high thermal conductivity ceramics described in the present application are required to have good thermal conductivity and suitable specific surface area, including but not limited to any one or more combinations of Si 3 N 4 , BN, and SiC. More specifically, they refer to inorganic ceramic materials with a thermal conductivity of not less than 30 W/m ⁇ °C, because the thermal conductivity of ⁇ -Al 2 O 3 is only 23 W/m ⁇ °C, and the thermal conductivity of other crystalline Al 2 O 3 generally does not exceed 23 W/m ⁇ °C.
  • the high thermal conductivity ceramics are selected from materials with a high thermal conductivity of more than 50 W/m ⁇ °C, such as ⁇ -SiC, ⁇ -Si 3 N 4 , and hexagonal BN.
  • ⁇ -SiC has a thermal conductivity of 146-270w/m ⁇ °C and a specific surface area of more than 20m 2 /g
  • ⁇ -Si 3 N 4 has a thermal conductivity of 30-155w/m ⁇ °C and a specific surface area of more than 40m 2 /g
  • hexagonal BN has a thermal conductivity of more than 79.54w/m ⁇ °C and a specific surface area of more than 50m 2 /g.
  • the titanium oxide is preferably rutile titanium dioxide or titanium dioxide containing rutile.
  • the carrier prepared after molding has high thermal conductivity and a large number of macropores, thereby improving the dissipation of heat generated during the reaction process, preventing the growth of ruthenium active component grains due to excessively high reaction temperature and the formation of agglomerates, which is beneficial to prolonging the service life of the catalyst.
  • the ruthenium active component described in the present application is derived from but not limited to any one or more combinations of the following components: RuCl 3 , RuCl 3 ⁇ xH 2 O, RuBr 3 , RuBr 3 ⁇ xH 2 O; chlororuthenates, such as K 3 RuCl 6 , (RuCl 3 ) 3- , K 2 RuCl 6 ; chlororuthenate hydrates, such as [RuCl 5 (H 2 O) 4 ] 2- , [RuCl 2 (H 2 O) 4 ] + ; ruthenates, such as K 2 RuO 4 or Na 2 RuO 4 ; ruthenium oxychloride, such as Ru 2 OCl 4 , Ru 2 OCl 5 , Ru 2 OCl 6 ; ruthenium oxychloride salts, such as K 2 Ru 2 OCl 10 , Cs 2 Ru 2 OCl 4 ; ruthenium ammine complexes, such as [Ru(NH 3 ) 6 ]
  • the active precious metal component ruthenium element accounts for 0.1-10wt% of the ruthenium catalyst, preferably 0.5-5wt%, more preferably 1-3%. A lower content of the active component will result in insufficient catalyst activity, while a higher content will increase the catalyst cost.
  • the amount of water added in step (2) is 20-50% of the mass of the mixed powder.
  • the drying in step (2) is performed at 60-120° C. for 3-24 hours.
  • the first calcination is to obtain a high-strength carrier for loading the ruthenium active component, mainly to optimize the porous morphology and physical properties of the carrier, while the second calcination is after step (3), and the thermal stability of the ruthenium active component must be considered.
  • the first calcination is calcined at 300-800°C for 1-24h, preferably calcined at 400-700°C for 3-6h.
  • the second calcination is calcined at 200-700°C for 1-24h, preferably calcined at 250-600°C for 2-6h, and then naturally cooled to room temperature.
  • the ruthenium catalyst of the present application should have a suitable specific surface area so as to maintain the catalytic activity and stability. Too high an area will cause insufficient stability. For this reason, the specific surface area of the carrier described in step (2) is controlled at 10-50m2 /g, which will cause the carrier to have difficulty in adsorbing active components, especially metal ruthenium, making it difficult for metal Ru to be evenly distributed on the carrier, resulting in low dispersion. For this reason, the impregnation solution also includes a surfactant, which is selected from any one of T-80 (Tween-80), OP-10 (alkylphenol polyoxyethylene ether), and PEG-400 (polyethylene glycol 400).
  • a surfactant which is selected from any one of T-80 (Tween-80), OP-10 (alkylphenol polyoxyethylene ether), and PEG-400 (polyethylene glycol 400).
  • the amount of the surfactant is 1-10 times the mass of the metal element in the ruthenium active component, preferably 1-5 times.
  • the ruthenium catalyst obtained after drying and two calcinations has a specific surface area of 10-50m2 /g, a pore size of 0.01-6um, a strength of 120-200N/cm when the diameter is 1.5-3mm, and a thermal conductivity of 0.6-2.0W/m ⁇ °C at 350°C based on the hot wire method.
  • the ruthenium catalyst provided in this application has high low-temperature activity.
  • the industrial production of hydrogen chloride oxidation to produce chlorine requires a catalytic temperature between 300-420°C, wherein a conversion rate of 50-80% can be basically guaranteed in the low temperature range of 300-330°C, and a conversion rate of not less than 90% can be achieved in the high temperature range of 360-420°C.
  • the ruthenium catalyst provided in this application can achieve a conversion rate of not less than 90% in the low temperature range.
  • the catalyst of the present application does not need to be activated before use, and the catalyst use conditions are: reaction pressure 0.1-0.5Mpa; reaction temperature 200-500°C, preferably 300-400°C; hydrogen chloride space velocity 1-5m 3 /kg-cat ⁇ h, oxygen to hydrogen chloride molar ratio 1:(4-1).
  • the obtained gas flow is passed through potassium iodide aqueous solution, and the sample is measured by iodine titration and neutralization titration to measure the amount of chlorine generated and the amount of unreacted hydrogen chloride, thereby calculating the conversion rate.
  • FIG1 is a TEM image of the ruthenium catalyst of Example 1-1.
  • FIG. 2 shows the particle size distribution of the ruthenium catalyst of Example 1-1.
  • FIG3 is a TEM image of the ruthenium catalyst of the control group 1-1.
  • FIG. 4 shows the particle size distribution of the ruthenium catalyst of the control group 1-1.
  • the surface area of ruthenium metal is tested by CO pulse adsorption method: the specific operation is to use Micrometric Chemisorb chemical adsorption instrument to perform CO pulse adsorption characterization analysis on the catalyst sample.
  • 50 mg of sample is filled into a U-shaped quartz tube, and a certain amount of quartz wool is placed at the bottom; Ar gas containing H2 is introduced and the temperature is raised at 5°C/min.
  • the temperature was raised to 350°C at a rate, and the pretreatment was carried out for 3 hours at this temperature and atmosphere.
  • the temperature was lowered to room temperature, and after the baseline was stabilized, a pulse of Ar containing CO was adsorbed until CO was saturated.
  • the ruthenium metal surface area in the embodiment was converted into the surface area per gram of metal ruthenium, and the unit was m2 /(g ⁇ Ru).
  • the ruthenium metal surface area test method in all embodiments was carried out under the same conditions.
  • Thermal conductivity determination There are different methods for determining thermal conductivity, and the results obtained by different test methods may also be different. This is related to the particle size of the test material, the loading speed, the loading method, etc. Even if the same test scheme is used, the results obtained by loading the same material with different particle sizes are different. In order to highlight the high thermal conductivity of the catalyst of the present application and its comparability with the control group, the following examples and the control group were tested under the same conditions.
  • the thermal conductivity of the catalyst is tested using the hot wire method, which assumes that there is an ideal infinitely thin and infinitely long linear heat source in the material.
  • the temperature rise of the hot wire over time is a function of the heating power and the thermal conductivity of the material being tested.
  • the temperature rise of the hot wire in the material being tested is measured using a thermocouple.
  • the thermal conductivity calculation formula for the tested sample is:
  • k is the thermal conductivity of the material being tested
  • d(In ⁇ )/d ⁇ is the logarithm of time-temperature change rate
  • Q is the heat flow rate transferred from the hot wire to the sample being tested. From the formula, we can know that as long as we know the heat flow rate Q transferred from the hot wire to the sample being tested and the temperature change rate at the selected point with time, we can calculate the thermal conductivity of the sample being tested.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 50%) with a diameter of 3 mm and a length of 5 mm, a strength of 120 N/cm, and a specific surface area of 30 m 2 /g.
  • the dried catalyst was dry-calcined in air at 200°C for 5 hours, the product was washed with water, and dried at 80°C to obtain the catalyst product.
  • the metal particle size was observed using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average particle size of the ruthenium, the active component of the catalyst prepared by this method was about 1.21 nm.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 30%) with a diameter of 3 mm and a length of 5 mm, a strength of 130 N/cm, and a specific surface area of 25 m 2 /g.
  • the dried catalyst was dry-calcined in air at 250°C for 4 hours; the product was washed with water and dried at 90°C to obtain the catalyst product.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 70%) with a diameter of 3 mm and a length of 5 mm, a strength of 138 N/cm, and a specific surface area of 30 m 2 /g.
  • a ruthenium chloride solution containing 1.5 grams of Ru was added with 3.8 grams of OP-10 to prepare 25 ml for impregnation, and then dried at 80°C for 10 hours to obtain a dried catalyst.
  • the dried catalyst was dry-calcined in air at 350°C for 3 hours; the product was washed with water and dried at 100°C to obtain the catalyst product.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 34%) with a diameter of 3 mm and a length of 5 mm, a strength of 142 N/cm, and a specific surface area of 50 m 2 /g.
  • the dried catalyst was dry-calcined in air at 350°C for 3 hours; the product was washed with water and dried at 110°C to obtain the catalyst product.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 34%) with a diameter of 3 mm and a length of 5 mm, a strength of 130 N/cm, and a specific surface area of 29 m 2 /g.
  • the dried catalyst was dry-calcined in air at 500°C for 3 hours; the product was washed with water and dried at 120°C to obtain the catalyst product.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 50%) with a diameter of 3 mm and a length of 5 mm, a strength of 150 N/cm, and a specific surface area of 18 m 2 /g.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 34%) with a diameter of 3 mm and a length of 5 mm, a strength of 150 N/cm, and a specific surface area of 29 m 2 /g.
  • the dried catalyst was dry-calcined in air at 450°C for 3 hours; the product was washed with water and dried at 120°C to obtain the catalyst product.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 34%) with a diameter of 3 mm and a length of 5 mm, a strength of 150 N/cm, and a specific surface area of 29 m 2 /g.
  • the dried catalyst was dry-calcined in air at 350°C for 3 hours; the product was washed with water and dried at 120°C to obtain the catalyst product.
  • a strip composite carrier composed of rutile titanium dioxide and ⁇ -alumina (titanium dioxide accounts for 34%) with a diameter of 3 mm and a length of 5 mm, a strength of 150 N/cm, and a specific surface area of 27 m 2 /g.
  • the dried catalyst was dry-calcined in air at 300°C for 3 hours; the product was washed with water and dried at 120°C to obtain the catalyst product.
  • a ruthenium catalyst was prepared as control group 1.
  • the specific steps are as follows: 3.23 grams of commercially available ruthenium oxide hydrate (RuCl 3 ⁇ nH 2 O, Ru content 37.3%) was dissolved in 21.9g of pure water, and stirred to obtain an aqueous solution of ruthenium chloride. The obtained aqueous solution was added dropwise to 40.0 grams of titanium oxide carrier to impregnate ruthenium chloride. The supported substance was dried at 60°C in air for 2 hours to obtain titanium oxide supported ruthenium chloride.
  • the obtained solid was heated from room temperature to 350°C in air for about 1 hour, and calcined at this temperature for 3 hours to obtain a spherical solid.
  • 0.5L of pure water was added to the obtained solid, stirred, and then placed for 30 minutes and washed by filtering. This operation was repeated 10 times. The washing time was about 7 hours.
  • the washed substance was dried at 60°C in air for 4 hours to obtain 41.1 grams of gray-black supported ruthenium oxide catalyst.
  • the calculated value of the ruthenium content of the control group 1-1 is 2.9% Ru/TiO 2
  • the measured value of the ruthenium metal surface area is 162.0 m 2 /(g ⁇ Ru).
  • the metal particle size was observed by transmission electron microscopy (TEM), as shown in Figure 3.
  • Figure 4 shows that the average particle size of the ruthenium catalyst prepared by this technology is 2.09 nm.
  • the supported material is dried at 60°C in air for 2 hours to obtain titanium oxide- ⁇ -alumina supported ruthenium chloride. Then, the obtained solid is heated from room temperature to 350°C in air for about 1 hour, and calcined at this temperature for 3 hours to obtain a spherical solid. 0.5L of pure water is added to the obtained solid, stirred, left for 30 minutes, and washed by filtration. Repeat this operation 5 times. The washing time is about 4 hours. The washed material is dried at 60°C in air for 4 hours to obtain 50.0 grams of gray-black supported ruthenium oxide catalyst.
  • the dried catalyst was dry-calcined in air at 250°C for 6 hours, the product was washed with water, and dried at 80°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the dried carrier was dry-baked in air at 500° C. for 4 hours to obtain a calcined strip carrier.
  • the dried catalyst was dry-baked in air at 280°C for 5 hours; the product was washed with water and dried at 90°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the dried carrier was dry-calcined in air at 550° C. for 4 hours to obtain a calcined strip-shaped carrier.
  • the dried catalyst was dry-calcined in air at 300°C for 4 hours; the product was washed with water and dried at 100°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 138N/cm, the specific surface area is 28m2 /g, the average pore size is 0.06um, and the thermal conductivity is 1.48W/m ⁇ °C at 350°C.
  • the dried carrier was dry-calcined in air at 650° C. for 4 hours to obtain a calcined strip-shaped carrier.
  • the dried catalyst was dry-calcined in air at 400°C for 2 hours; the product was washed with water and dried at 110°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 142N/cm
  • the specific surface area is 50m2 /g
  • the average pore size is 0.1um
  • the thermal conductivity coefficient tested at 350°C is 1.32W/m ⁇ °C.
  • the dried carrier was dry-baked in air at 700° C. for 4 hours to obtain a calcined strip carrier.
  • the dried catalyst was dry-calcined in air at 350°C for 4 hours to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 118N/cm, the specific surface area is 26m2 /g, the average pore size is 0.07um, and the thermal conductivity is 1.29W/m ⁇ °C at 350°C.
  • the mass percentage of metal ruthenium is:
  • the dried catalyst was dry-calcined in air at 400°C for 3 hours to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 143N/cm, the specific surface area is 24m2 /g, the average pore size is 1.0um, and the thermal conductivity coefficient tested at 350°C is 1.23W/m ⁇ °C.
  • the dried carrier was dry-calcined in air at 650° C. for 4 hours to obtain a calcined strip-shaped carrier.
  • the dried catalyst was dry-calcined in air at 350°C for 2 hours; the product was washed with water and dried at 120°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 129N/cm, the specific surface area is 20m2 /g, the average pore size is 0.6um, and the thermal conductivity coefficient tested at 350°C is 1.45W/m ⁇ °C.
  • the dried carrier was dry-calcined in air at 650° C. for 4 hours to obtain a calcined strip-shaped carrier.
  • the dried catalyst was dry-calcined in air at 300°C for 3 hours; the product was washed with water until there was no chloride ion, and dried at 120°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 121N/cm, the specific surface area is 27m2 /g, the average pore size is 0.09um, and the thermal conductivity is 1.28W/m ⁇ °C at 350°C.
  • the dried catalyst was dry-calcined in air at 350°C for 3 hours; the product was washed with water and dried at 120°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 139N/cm, the specific surface area is 42m2 /g, the average pore size is 0.04um, and the thermal conductivity coefficient tested at 350°C is 1.22W/m ⁇ °C.
  • the dried carrier was dry-baked in air at 600°C for 4 hours to obtain a strip-shaped carrier with a strength of 153 N/cm, a specific surface area of 25 m 2 /g, and an average pore size of 0.9 um.
  • the dried catalyst was dry-calcined in air at 280°C for 3 hours; the product was washed with water and dried at 120°C to obtain the catalyst product.
  • the mass percentage of metal ruthenium is:
  • the final catalyst strength is 151N/cm, the specific surface area is 25m2 /g, the average pore size is 0.03um, and the thermal conductivity coefficient tested at 350°C is 1.52W/m ⁇ °C.
  • the obtained solid was heated from room temperature to 350°C in air for about 1 hour, and calcined at this temperature for 3 hours to obtain a spherical solid.
  • 0.5L of pure water was added to the obtained solid, stirred, and allowed to stand for 30 minutes and washed by filtering. This operation was repeated 5 times. The washing time was about 4 hours.
  • the washed material was dried at 60°C in air for 4 hours to obtain 50.0 grams of gray-black supported ruthenium oxide catalyst.
  • the overall activity of the catalysts prepared in Examples 2-1 to 2-12 is higher than that of the control group.
  • the conversion rate in the high temperature range and the life of the catalyst at high temperatures are significantly improved.

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Abstract

La présente demande se rapporte au domaine des catalyseurs, et en particulier à un catalyseur à base de ruthénium à dispersité élevée d'oxydation du chlorure d'hydrogène pour préparer du chlore et son procédé de préparation. Le procédé comprend les étapes suivantes : imprégnation, avec un liquide d'imprégnation pré-mélangé avec un tensioactif, d'un support composite préparé au moyen de l'utilisation d'oxyde de titane et d'oxyde d'aluminium ou d'un support poreux préparé au moyen de l'utilisation d'oxyde de titane, de céramique à conductivité thermique élevée et d'un agent auxiliaire, et soumission de celui-ci à des procédés tels que le séchage, la calcination, le refroidissement, le lavage à l'eau et le séchage, de façon à obtenir le catalyseur à base de ruthénium. Le catalyseur de la présente demande améliore la dispersité de métal, réduit la quantité d'utilisation de métal actif, et présente une stabilité thermique élevée, ce qui permet de prolonger la durée de vie du catalyseur.
PCT/CN2024/094092 2023-05-22 2024-05-18 Catalyseur à base de ruthénium à dispersité élevée d'oxydation du chlorure d'hydrogène pour préparer du chlore et son procédé de préparation Pending WO2024240099A1 (fr)

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CN202310575342.5A CN116899558B (zh) 2023-05-22 2023-05-22 一种热稳定性的高导热钌催化剂及其制备方法
CN202310574910.XA CN116550321A (zh) 2023-05-22 2023-05-22 一种用于氯化氢氧化制氯气的高分散度钌催化剂及其制备方法
CN202310574910.X 2023-05-22
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6991772B1 (en) * 1995-05-31 2006-01-31 The United States Of America As Represented By The Secretary Of The Air Force H2O2 decomposition catalyst
CN101316656A (zh) * 2005-11-30 2008-12-03 住友化学株式会社 担载钌的制造方法和氯的制造方法
CN109453764A (zh) * 2018-11-16 2019-03-12 西安元创化工科技股份有限公司 用于氯化氢氧化制氯气的二氧化钌催化剂及其制备方法
CN115155632A (zh) * 2022-06-24 2022-10-11 西安近代化学研究所 一种氯化氢氧化催化剂的制备方法
CN116550321A (zh) * 2023-05-22 2023-08-08 康纳新型材料(杭州)有限公司 一种用于氯化氢氧化制氯气的高分散度钌催化剂及其制备方法
CN116899558A (zh) * 2023-05-22 2023-10-20 康纳新型材料(杭州)有限公司 一种热稳定性的高导热钌催化剂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6991772B1 (en) * 1995-05-31 2006-01-31 The United States Of America As Represented By The Secretary Of The Air Force H2O2 decomposition catalyst
CN101316656A (zh) * 2005-11-30 2008-12-03 住友化学株式会社 担载钌的制造方法和氯的制造方法
CN109453764A (zh) * 2018-11-16 2019-03-12 西安元创化工科技股份有限公司 用于氯化氢氧化制氯气的二氧化钌催化剂及其制备方法
CN115155632A (zh) * 2022-06-24 2022-10-11 西安近代化学研究所 一种氯化氢氧化催化剂的制备方法
CN116550321A (zh) * 2023-05-22 2023-08-08 康纳新型材料(杭州)有限公司 一种用于氯化氢氧化制氯气的高分散度钌催化剂及其制备方法
CN116899558A (zh) * 2023-05-22 2023-10-20 康纳新型材料(杭州)有限公司 一种热稳定性的高导热钌催化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RONG CHENG: "Effect of the Preparing Method of the Supporter and Catalyst on the Characters of the Activated Carbon Supported Ruthenium Catalyst for Ammonia Synthesis", CHINA MASTER'S THESES FULL-TEXT DATABASE, ENGINEERING SCIENCES I, 1 May 2005 (2005-05-01), XP093241811 *

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