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WO2024240099A1 - 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 - Google Patents

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 Download PDF

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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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French (fr)
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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/zh
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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

本申请涉及催化剂领域，特别涉及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。利用氧化钛、氧化铝制备获得的复合载体或者氧化钛、高导热陶瓷和助剂制备的多孔载体，通过浸渍预混合有表面活性剂的浸渍液，经烘干、煅烧、冷却、水洗、烘干等工艺，获得钌催化剂。本申请的催化剂提高了金属分散度，降低了活性金属的使用量，热稳定性高从而延长了催化剂的使用寿命。

Description

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 技术领域
本申请涉及催化剂领域，特别涉及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。
背景技术
氯气是一种重要的化工基础原料，广泛应用于化学、冶金、造纸、纺织、石油化工、饮用水消毒和环保等行业。在工业上生产有机氯产品时会产生大量副产物氯化氢，原子利用率最大在50％，这些氯化氢气体大多用水吸收制成盐酸，但其中含有有机杂质，用途受到限制。随着人们环保意识的增强，对于氯气、氯化氢等有毒、强腐蚀性物质的运输管理和排放等要求越来越严格，副产氯化氢变得越来越难以处理。将氯化氢转化制备氯气，可实现氯资源闭路循环利用，是处理回收副产氯化氢最为有效的方法，并已在涉氯行业中形成高度共识。
催化氧化法是最有效的解决方案，尤其是经由Deacon反应的催化氧化法，由于操作简单、设备成本低的特点，最具工业化潜力。在Deacon于1868年开发的将氯化氢催化氧化的方法中，将氯化氢通过氧气放热平衡氧化为氯气。氯化氢转化为氯气使得氯气生产可与通过氯碱电解而进行的氢氧化钠生产分离。所述分离是十分具有吸引力的，因为氯气的世界需求量是高于氢氧化钠的。
Deacon反应最为核心的因素是催化剂，自铜基催化剂(Deacon催化剂)后，铁、铬等过渡金属催化剂相继推出。近年来又发展了高活性的钌基(Ru)、铈基(Ce)以及复合氧化物催化剂。铜系催化剂因较低成本而备受关注，清华大学的中国专利申请，公开号：CN101125297A，名称“一种氧氯化催化剂及其应用”中使用铜和氧化物惰性载体，但随着高温下反应时间推移，铜粒子会聚集，且颗粒间形成桥接，造成催化剂比表面积大幅下降，使得活性下降，从而导致失活。含铜的氯化氢氧化催化剂可采用对氯化氢氧化反应体系惰性的载体进行负载，如美国专利申请US4123389A采用硅胶、氧化铝或氧化钛作为载体，铜为主要活性组分，但制备过程需有机溶剂浸渍，环境污染大。
铬催化剂虽然活性良好，但铬剧毒，大量使用对环境影响不利。美国专利US5716592A报道采用铬氧化物和稀土铈复合的催化剂，装填量45g催化剂，HCl流量0.3L/min，O2流量0.225L/min，在380℃下催化氧化氯化氢，氯化氢的转化率最高可达85.2％。由于铬有毒性，且易与氯气形成低沸点的氧氯化铬，容易使催化剂失活。
有关钌催化剂用于氯化氢氧化催化技术，住友化学株式会社的中国专利申请 CN1182717A、CN1150127C和CN1272238C中公开了浸渍氧化钌和基于TiO2、ZrO2等氧化物作为载体煅烧制备钌基催化剂。此外，拜耳材料科学(Bayer Materialscience AG)的WO2007/134772A1公开了含有二氧化锡的含钌基催化体系。
尽管相较于其它催化剂，钌基催化剂具有用量少和低温活性高的特点，例如CN1182717A中将RuO2和SiO2负载到TiO2上制备的钌基催化剂具有更好的低温催化性能。但由于反应放热效应的存在，活性组分RuO2颗粒因热消散不足易导致烧结，长时间使用后，该催化剂依然存在反应活性下降的问题。
住友化学的CN1272238C公开了负载在金红石型TiO2和α-氧化铝复合载体上的RuO2催化剂将Deacon过程的反应温度降至300℃左右，理论平衡转化率提高至90％-95％。但在实际使用过程发现当温度高于360℃，尤其当温度达到390℃以上时，转化率大幅下降到80％以下。钌基催化剂与其它非贵金属催化剂相比主要有两个优势：第一，其300-350℃的低温活性好，HCl平衡转化率高；第二，其表面活性相的氯化具有自限性，催化剂不会因过度氯化而生成易挥发的氯化物。然而，由于贵金属价格较高，一定程度上降低了该过程的经济效益，同时钌耐高温性较差，在360-390℃的高温尤其在温度高于400℃时易失活。目前本领域研究人员致力于改进钌基催化剂，通过进一步提高其活性和高温热稳定性，降低成本以实现更广泛的商业化。住友化学的CN101223104A采用不同比例混合的金红石二氧化钛和α-氧化铝为载体，制备得到负载型RuO2催化剂。该催化剂在氯化氢氧化过程中活性不断降低，需要逐渐升高反应温度来提高氯化氢转化率，同时高温下加速活性降低。
Deacon反应温度一般280-420℃之间，处于较高热环境下，同时由于该反应属于放热反应，因此在需要催化剂不仅拥有良好的导热性和热稳定性，而且要有较低的比表面积，如10-50m2/g。由于材料受热效应影响，具有大比表面积的材料在高温下随着晶粒长大，孔结构发生改变会使得比表面积减小。这对负载活性组分后的催化剂是十分不利的，会造成活性下降，加速失活。
催化剂活性组分晶粒大小和分散度极大影响反应的活性，金属粒径越小，可以做到较金属高分散，同时可以和载体有较好的结合，晶粒不易长大，具有更好的热稳定性。通常在制备催化剂时会选择高比表面积材料作为载体，这有利于对活性金属的负载以及较高的分散度。Deacon反应由于反应条件的限制，需要热稳定性好的载体，选取较小比表面积的材料作为载体，这会导致活性组分钌难以做到高分散，不仅影响催化剂活性，也会增加钌的用量，不利于成本的控制。
发明内容
本申请的目的是提供一种用于氯化氢氧化制氯气的催化剂，活性组分钌为高分散态；还在于提供一种高载体导热率的钌催化剂；所述催化剂的制备方法及其用于将氯化氢通过氧气催化氧化为氯气。
一方面，本申请的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法包括如下步骤：
(1)将含钌活性组分通过表面活性剂分散，制成浸渍液的工序；
(2)将所述浸渍液接触附着于氧化钛和氧化铝的复合载体上，干燥后煅烧的工序，煅烧温度在150-700℃，时间为1-24小时；
(3)冷却、水洗，烘干。
本领域在钌活性组分负载载体的成分、载体比表面积、生产制备过程中诸如温度、时间等参数上都有相关研究，但并没有对钌活性组分的分散性，钌晶粒大小或浸渍液预处理等方面进行探索。
其中，所述表面活性剂选自包括但不限于聚氧乙烯型非离子表面活性剂、聚乙二醇、聚山梨酯等亲水型非离子表面活性剂的任意一种或多种的组合。更具体地说，所述表面活性剂选自T-80(吐温-80)、OP-10(烷基酚聚氧乙烯醚)、PEG-400(聚乙二醇400)中的任意一种或多种的组合；更优选地采用T-80作为表面活性剂。通过添加表面活性剂，形成对活性组分钌粒子间的包覆隔离，钌组分在浸渍吸附或在烘干阶段钌粒子间的不会产生严重团聚，使得作为活性组分的贵金属钌(Ru)处于高分散态，进而抑制因煅烧使得金属粒子长大导致结块。
优选的，所述表面活性剂的用量为钌活性组分中金属元素质量的1-10倍，更优选为1-5倍。
本申请所述的钌活性组分来源于但不限于以下组分的任意一种或多种的组合：RuCl3、RuCl3·xH2O、RuBr3、RuBr3·xH2O；氯钌酸盐，如K3RuCl6、(RuCl3)3-、K2RuCl6；氯钌酸盐水合物，如[RuCl5(H2O)4]2-、[RuCl2(H2O)4]+；钌酸盐，如K2RuO4或Na2RuO4；氯氧化钌，如Ru2OCl4、Ru2OCl5、Ru2OCl6；氯氧化钌盐，如K2Ru2OCl10、Cs2Ru2OCl4；钌氨配合物，如[Ru(NH3)6]2+、[Ru(NH3)6]3+、[Ru(NH3)5H2O]2+；氯化钌胺络合物，如[Ru(NH3)5Cl]2+、[Ru(NH3)6]Cl2、[Ru(NH3)6]Cl3；溴化钌胺络合物，如[Ru(NH3)6]Br3；乙酰丙酮钌；羰基钌，如Ru(CO)5或Ru(CO)12；钌的有机酸盐，如[Ru3O(OCOCH3)6(H2O)3]OCOCH3、Ru2(RCOO)4Cl(其中R为含1-3个碳的烃基)；亚硝酰基硝酸钌，如K2[RuCl6(NO)]、[Ru(NH3)5(NO)]Cl3、[Ru(OH)(NH3)4(NO)](NO3)2、Ru(NO)(NO3)3；钌磷配合物等。优选地，所述钌活性组分选自三氯化钌或其水合物、三溴化钌或其水合物。更优选的化合物为三氯化钌水合物。
本申请中活性贵金属组分钌元素占所述钌催化剂为0.1-10wt％，更优选为0.5-5wt％，最优选为1-3wt％。活性组分含量较低则会导致催化剂活性不够，含量过高则会增加催化剂成本。
优选的，所述步骤(2)中的浸渍方式为等体积浸渍、过量浸渍、喷洒浸渍的任意一种。
优选的，所述氧化钛优选为金红石型二氧化钛。所述氧化铝选为α-Al2O3，且具有不低于23W/m·℃的导热系数。通过将金红石型二氧化钛与具有高导热系数α-Al2O3的形成复合载体，成型后制备出的载体具有高导热性能和较多的大孔，进而提高反应过程产生热量的散除，防止因反应温度过高导致钌活性组分晶粒的生长进而形成结块，同时还有利于实现钌活性组分的高分散态。现有技术大多数载体仍具有一定的反应惰性，且比表面积不易改善，导致对金属钌的吸附较为困难。本申请提供的复合载体在上述表面活性剂的预处理下，对金属钌的吸附得以显著改善。
所述复合载体通过成型工艺制备获得，其形状包括粉末状、球形、柱状、异型、蜂窝状的任意一种或多种的组合。
载体浸渍、成型后制备获得的催化剂，具有10-50m2/g的比表面积，钌晶粒在1-10nm，钌金属表面积在120-410m2/(g·Ru)，呈高分散态，同时制备过程强化热稳定性，有利于延长使用寿命，满足工业化催化、生产的要求。
本申请通过制备工艺的改进，在较低比表面积载体上制备出较已有催化剂具有更高钌分散度的催化剂。经测试目前已工业化1.5％Ru含量催化剂，金属钌表面积约130-200m2/(g·Ru)，而本申请方法制备的催化剂1.5％Ru同等含量下表面积可以达到200-340m2/(g·Ru)。高的分散度增加了钌原子的有效利用率，优异的提高了催化剂活性，可以实现在较低金属负载量的条件下具有较高活性。
优选的，本申请在载体成型工艺后负载钌活性组分，负载后煅烧不会引起明显烧结，可有效防止金属晶粒长大，从而制备出高分散度的催化剂。
本申请中所选载体材料具有耐酸耐碱，高温性能稳定的特点，其中高导热系数材料的选择有利于反应热量的及时散除，合适的比表面积有利于活性金属的分散。本申请提供的钌催化剂用于氯化氢氧化制备氯气，催化活性好，低温时也具有较高的催化活性。通过表面活性剂加入钌活性组分形成浸渍液，有利于提高载体对活性金属的吸附，改善金属钌的分散度。同时可在后续的干燥、煅烧等过程防止钌组分迁移和团聚。高的分散度意味着金属原子有效利用率增大，具有高活性，在保持高转化率的同时，降低了金属含量，有利于降低催化剂成本。
另一方面，本申请提供的一种钌催化剂，包括多孔载体和浸渍于所述多孔载体中的 钌活性组分；所述多孔载体来源于氧化钛、高导热陶瓷和助剂混合物，所述高导热陶瓷选自Si3N4、BN、SiC中的任意一种或多种的组合。
本申请所述的高导热陶瓷要求具有较好的导热性和合适的比表面积，包括但不限于Si3N4、BN、SiC中的任意一种或多种的组合，更确切地说，是指不低于30W/m·℃导热系数的无机陶瓷材料，因为α-Al2O3的导热系数仅仅为23W/m·℃，其他晶型的Al2O3导热系数一般不超过23W/m·℃，通过对载体组分导热性和表面积的改良，将极显著地提高载体高温环境下的转化率。更优选地，所述高导热陶瓷选自β-SiC、β-Si3N4、六方晶型BN等可能大于50W/m·℃高导热系数的材料。其中，β-SiC具有146-270w/m·℃的热导系数及20m2/g以上的比表面积，β-Si3N4具有30-155w/m·℃的热导系数及40m2/g以上的比表面积，六方晶型BN具有79.54w/m·℃以上的热导率及50m2/g以上的比表面积。
另外，所述氧化钛优选为金红石型二氧化钛或包含金红石型的二氧化钛。本申请通过将金红石型二氧化钛与高导热材料复合，成型后制备出的载体具有高导热性能和较多的大孔，进而提高反应过程产生热量的散除，防止因反应温度过高导致钌活性组分晶粒的生长进而形成结块，有利于延长催化剂使用寿命。
本申请所述的钌活性组分来源于但不限于以下组分的任意一种或多种的组合：RuCl3、RuCl3·xH2O、RuBr3、RuBr3·xH2O；氯钌酸盐，如K3RuCl6、(RuCl3)3-、K2RuCl6；氯钌酸盐水合物，如[RuCl5(H2O)4]2-、[RuCl2(H2O)4]+；钌酸盐，如K2RuO4或Na2RuO4；氯氧化钌，如Ru2OCl4、Ru2OCl5、Ru2OCl6；氯氧化钌盐，如K2Ru2OCl10、Cs2Ru2OCl4；钌氨配合物，如[Ru(NH3)6]2+、[Ru(NH3)6]3+、[Ru(NH3)5H2O]2+；氯化钌胺络合物，如[Ru(NH3)5Cl]2+、[Ru(NH3)6]Cl2、[Ru(NH3)6]Cl3；溴化钌胺络合物，如[Ru(NH3)6]Br3；乙酰丙酮钌；羰基钌，如Ru(CO)5或Ru(CO)12；钌的有机酸盐，如[Ru3O(OCOCH3)6(H2O)3]OCOCH3、Ru2(RCOO)4Cl(其中R为含1-3个碳的烃基)；钌-亚硝酰基配合物，如K2[RuCl6(NO)]、[Ru(NH3)5(NO)]Cl3、[Ru(OH)(NH3)4(NO)](NO3)2、Ru(NO)(NO3)3；钌磷配合物等。优选地，所述钌活性组分选自三氯化钌或其水合物、三溴化钌或其水合物。更优选的化合物为三氯化钌水合物。
本申请中活性贵金属组分钌元素占所述钌催化剂的0.1-10wt％，优选0.5-5wt％，更优选1-3％。活性组分含量较低则会导致催化剂活性不够，含量过高则会增加催化剂成本。
为了获得所述的钌催化剂，本申请提供了相应的制备方法，具体包括如下步骤：
(1)将氧化钛、高导热材料和助剂混合，获得混合粉体；
(2)所述混合粉体与水混合，成型、烘干，经第一次煅烧获得高强度载体；
(3)将钌活性组分前驱体溶液制备成浸渍液；
(4)将所述浸渍液浸渍于高强度载体上，烘干，经第二次煅烧后获得所述钌催化剂；
其中，所述高导热材料选自Si3N4、BN、SiC中的任意一种或多种的组合。更优选的，所述高导热陶瓷选自β-SiC、β-Si3N4、六方晶型BN等可能大于50W/m·℃高导热系数的材料。
本申请利用钌活性组分前驱体制成的浸渍液负载到高强度载体上，需考量载体的耐酸性、耐碱性、高热稳定性，选择合适的比表面积有利于活性金属的分散。
载体形状选自包括但不限于球状、圆柱状、蜂窝状、异型结构等。
合适的成型工艺将提供更大的反应比表面积。成型方法包括将粉末载体经成型工艺获得固体颗粒，再经烘干煅烧工艺得到成型后的载体。所述的成型工艺选自包括但不限于压片、滚球、挤条、喷雾成型、油柱成型。优选挤条、压片、滚球成型工艺，更优选挤条成型。作为一种优选的挤条成型工艺，挤出成型的高强度载体颗粒直径1-3mm，长度2-7mm。
优选的，所述步骤(1)中所述助剂占混合粉体总重的1-10wt％，所述步骤(2)中氧化钛占煅烧后载体总重的20-80％。更优选地，所述氧化钛占载体总重的30-60％，助剂占混合粉体总重的1-10wt％。所述氧化钛优选为金红石型二氧化钛。
优选的，所述助剂选自聚乙烯醇、纤维素、淀粉、田菁粉、合成树脂的任意一种或多种的组合，优选采用纤维素或田菁粉。其中，所述纤维素选自包括但不限于甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素的任意一种或多种的组合。所述助剂均为有机粘结剂，帮助混合粉体在成型工艺中提高成型效果；并使其在干燥、煅烧后形成细孔，提高比表面积。
优选的，所述步骤(2)中的加水量为所述混合粉体质量的20-50％。所述步骤(2)中的烘干是在60-120℃内烘干3-24h。
本领域技术人员根据所选用的助剂和载体期望达到的细孔形态和比表面积，可进行适应性调整，均在本申请保护范围内。
所述第一次煅烧是为了获得高强度载体用于负载钌活性组分，以优化载体多孔形态和物理性能为主，而第二次煅烧是在步骤(3)之后，须考虑钌活性组分热稳定性问题。为此，所述第一次煅烧是在300-800℃内煅烧1-24h，优选是在400-700℃内煅烧3-6h。所述第二次煅烧是在200-700℃内煅烧1-24h，优选是在250-600℃内煅烧2-6h，然后自然冷却至室温。
所述步骤(4)之后，可进一步水洗去除灰分，在60-120℃烘干即得钌催化剂产品。
本申请钌催化剂应当具备合适的比表面积从而有利于保持催化活性和稳定性，比表 面积过高会引起稳定性的不足。为此步骤(2)所述的载体比表面积控制在10-50m2/g，这会引起载体对活性组分尤其是金属钌的吸附较为困难，使得金属Ru在载体上难以分布均匀，导致分散度较低。为此，所述浸渍液中还包括表面活性剂，所述表面活性剂选自包括但不限于T-80(吐温-80)、OP-10(烷基酚聚氧乙烯醚)、PEG-400(聚乙二醇400)中的任意一种。所述表面活性剂的用量为钌活性组分中金属元素质量的1-10倍，优选1-5倍。通过表面活性剂对浸渍液进行处理，可以在烘干、煅烧过程防止钌组分迁移和团聚，生成更细的钌晶粒，更有利于提高钌的分散度。
经过烘干和两次煅烧后获得的钌催化剂，具有10-50m2/g的比表面积，孔径为0.01-6um，直径为1.5-3mm时强度为120-200N/cm，基于热线法在350℃时导热率为0.6-2.0W/m·℃。
本申请提供的钌催化剂具有较高的低温活性。氯化氢氧化制氯气，工业生产要求催化温度在300-420℃之间，其中在低温区间300-330℃能基本保证50-80％的转化率，在高温区间360-420℃能实现不低于90％的转化率。本申请提供的钌催化剂能实现在低温区间不低于90％的转化率。
本申请的催化剂使用前无需活化，催化剂使用条件为：反应压力0.1-0.5Mpa；反应温度200-500℃，优选300-400℃；氯化氢空速1-5m3/kg-cat·h，氧气与氯化氢摩尔比1:(4-1)。将所得气流通过碘化钾水溶液，取样通过碘滴定法和和中和滴定法测得氯的生成量和未反应的氯化氢量，由此计算转化率。
附图说明
图1为实施例1-1钌催化剂的TEM图。
图2为实施例1-1钌催化剂的粒径分布。
图3为对照组1-1钌催化剂的TEM图。
图4为对照组1-1钌催化剂的粒径分布。
具体实施方式
下面根据实例详细描述本申请，需要说明的是，下面描述的实施例对有经验的人来说是示例性的，旨在用于解释本申请，但本申请不限于这些实例。在未经特殊说明的情况下，所有百分比单位应理解为质量百分比。
钌金属表面积测试方法采用CO脉冲吸附法进行测试：具体操作为使用Micrometric Chemisorb型化学吸附仪对催化剂样品进行CO脉冲，吸附表征分析。将50mg样品装填至U型石英管中，其底部垫有一定量的石英棉；通入含有H2的Ar气，以5℃/min升温 速率升到350℃，在此温度和气氛下进行预处理3h。降至室温，待基线稳定后以含CO的Ar脉冲吸附，直至CO饱和。得到CO吸附量后，根据Ru/CO＝1:1原子比进行计算即可得到钌金属表面积。实施例中钌金属表面积折算成每克金属钌的表面积，单位为m2/(g·Ru)。所有实施例中钌金属表面积测试方法均在相同条件下进行。
导热系数测定：导热系数的测定有不同方法，不同测试方法得出的结果可能也不相同。这和测试物料颗粒大小、装填速度、装填方式等有关，即使同样的测试方案，同一种物料不同粒度的装填，所得到的结果也不相同。为了突出本申请催化剂的高导热率的以及和对照组的可比性，以下实施例和对照组均在相同条件下进行测试。
催化剂导热系数采用热线法进行测试，即是假定在材料中存在一个理想的无限细且无限长的线形热源，热线随时间变化的温升是加热功率和被测材料导热系数的函数，用热电偶测量被测材料中热线的温升。被测试样的导热系数计算式为：
式中，k为被测材料的导热系数；d(Inτ)/dθ为在时间对数-温度变化率；Q为热线传给被测试样的热流率。由公式可知，只要知道通过热线传给被测试样的热流率Q以及所选点处温度随时间的变化率，就可以计算出被测试样的导热系数。
实施例1-1
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比50％)组成的直径3mm，长度5mm条形复合载体50克，强度120N/cm，比表面积为30m2/g。
用含Ru 0.75克的氯化钌溶液加入1.5g的吐温-80配成25毫升进行浸渍，并于60℃干燥12小时，得干燥后的催化剂。
将干燥后的催化剂于空气中200℃干煅烧5小时，将产品用水洗，80℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：1.5％Ru/(TiO2:Al2O3＝50:50)，钌金属表面积测试值306.7m2/(g·Ru)。
如图1所示，采用透射电镜(TEM)对金属粒径进行观察。如图2所示，采用本方法制备出的催化剂活性组分钌粒径平均约1.21nm。
实施例1-2
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比30％)组成的直径3mm，长度5mm条形复合载体50克，强度130N/cm，比表面积为25m2/g。
用含Ru 0.5克的亚硝酰基硝酸钌溶液加入0.5g的吐温-80配成25毫升进行浸渍， 并于80℃干燥6小时，得干燥后的催化剂；
将干燥后的催化剂于空气中250℃干焙烧4小时；将产品用水洗，90℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：1.0％Ru/(TiO2:Al2O3＝30:70)，钌金属表面积测试值281.0m2/(g·Ru)。
实施例1-3
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比70％)组成的直径3mm，长度5mm条形复合载体50克，强度138N/cm，比表面积为30m2/g。
用含Ru1.5克的氯化钌溶液加入3.8g的OP-10配成25毫升进行浸渍，并于80℃干燥10小时，得干燥后的催化剂。
将干燥后的催化剂于空气中350℃干煅烧3小时；将产品用水洗，100℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：3.0％Ru/(TiO2:Al2O3＝70:30)，钌金属表面积测试值260.0m2/(g·Ru)。
实施例1-4
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比34％)组成的直径3mm，长度5mm条形复合载体50克，强度142N/cm，比表面积为50m2/g。
用含Ru 1.0克的氯化钌溶液加入2.0g的吐温-80配成30毫升进行浸渍，并于80℃干燥10小时，得干燥后的催化剂。
将干燥后的催化剂于空气中350℃干煅烧3小时；将产品用水洗，110℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：2.0％Ru/(TiO2:Al2O3＝34:66)，钌金属表面积测试值325.0m2/(g·Ru)。
实施例1-5
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比34％)组成的直径3mm，长度5mm条形复合载体50克，强度130N/cm，比表面积为29m2/g。
取焙烧后的载体50克，用含Ru 0.75克的亚硝酰基硝酸钌溶液加入4.0g的PEG-400配成30毫升进行浸渍，并于100℃干燥7小时，得干燥后的催化剂。
将干燥后的催化剂于空气中400℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：1.5％Ru/(TiO2:Al2O3＝34:66)，钌金属 表面积测试值326.7m2/(g·Ru)。
实施例1-6
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比80％)组成的直径3mm，长度5mm条形复合载体50克，强度150N/cm，比表面积为18m2/g。
取焙烧后的载体50克，用含Ru 0.4克的亚硝酰基硝酸钌溶液加入5.0g的PEG-400配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中500℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为:0.8％Ru/(TiO2:Al2O3＝80:20)，钌金属表面积测试值297.5m2/(g·Ru)。
实施例1-7
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比50％)组成的直径3mm，长度5mm条形复合载体50克，强度150N/cm，比表面积为18m2/g。
取焙烧后的载体50克，用含Ru 0.5克的氯氧化钌酸钾溶液加入2.0g的吐温-80配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中400℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为:1.0％Ru/(TiO2:Al2O3＝50:50)，钌金属表面积测试值300.0m2/(g·Ru)。
实施例1-8
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比34％)组成的直径3mm，长度5mm条形复合载体50克，强度150N/cm，比表面积为29m2/g。
取焙烧后的载体50克，用含Ru 0.75克的氯钌酸钾溶液加入3.0g的吐温-80配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中450℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为:1.5％Ru/(TiO2:Al2O3＝34:66)，钌金属表面积测试值286.7m2/(g·Ru)。
实施例1-9
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比34％)组成的直径3mm，长度5mm条形复合载体50克，强度150N/cm，比表面积为29m2/g。
取焙烧后的载体50克，用含Ru 1.0克的钌氨配合物溶液加入3.0g的OP-10配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中350℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为:2％Ru/(TiO2:Al2O3＝50:50)，钌金属表面积测试值305.0m2/(g·Ru)。
实施例1-10
称取由金红石型二氧化钛和α-型氧化铝(氧化钛占比34％)组成的直径3mm，长度5mm条形复合载体50克，强度150N/cm，比表面积为27m2/g。
取焙烧后的载体50克，用含Ru 0.5克的钌氨配合物溶液加入1.5g的OP-10配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中300℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为:1％Ru/(TiO2:Al2O3＝50:50)，钌金属表面积测试值410.0m2/(g·Ru)。
对照组1-1
根据中国发明专利CN1245773A实施例4公布的制备方法制备钌催化剂，作为对照组1，具体步骤如下：将市售的氧化钌水合物(RuCl3·nH2O，Ru含量37.3％)3.23克溶解于21.9g纯水中，搅拌后得至氯化钌水溶液。将所得的水溶液滴加到40.0克由氧化钛载体上，浸渍氯化钌。将载持的物质在空气中60℃干燥2小时，得到氧化钛载持氯化钌。然后，将得到的固体在空气中大约经l小时从室温升至350℃，并在该温度烧成3小时得到球状固体。在得到的固体中加入0.5L的纯水搅拌后放置30min并通过过滤进行水洗。重复进行10次该操作。水洗时间大约为7小时。将水洗的物质在空气中60℃干燥4h得到41.1克灰黑色负载氧化钌催化剂。
对照组1-1金属钌含量的计算值是2.9％Ru/TiO2，钌金属表面积测试值162.0m2/(g·Ru)。采用透射电镜(TEM)对金属粒径进行观察，如图3所示。图4展示了该技术制备出的催化剂钌的平均粒径为2.09nm。
对照组1-2
根据中国发明专利CN1245773A实施例18公布的制备方法制备钌催化剂，作为对照组2，具体步骤如下：将市售的氧化钌水合物(RuCl3·nH2O，Ru含量37.3％)2.03克溶解于14.6g纯水中，搅拌后得至氯化钌水溶液。将所得的水溶液滴加到50.0克由氧化 钛-α-氧化铝(氧化钛占比50％)组成的条形复合载体上，浸渍氯化钌。将载持的物质在空气中60℃干燥2小时，得到氧化钛-α-氧化铝载持氯化钌。然后，将得到的固体在空气中大约经l小时从室温升至350℃，并在该温度烧成3小时得到球状固体。在得到的固体中加入0.5L的纯水搅拌后放置30min并通过过滤进行水洗。重复进行5次该操作。水洗时间大约为4小时。将水洗的物质在空气中60℃干燥4h得到50.0克灰黑色负载氧化钌催化剂。对照组1-2金属钌含量的计算值是1.5％Ru/(TiO2:Al2O3＝50:50)，钌金属表面积测试值166.7m2/(g·Ru)。
试验例1-1
将所有实施例和对照组催化剂的活性在固定床催化反应器上进行；反应器类型：石英管管式反应器，内径25mm；催化剂粒度为颗粒，用量为10g；主要反应条件为：HCl以0.76L/min，O2以0.64L/min通过催化剂床层。不同温度下转化率见表1和表2，实施例1-1至实施例1-10与对照组1-1、对照组1-2在相同条件下进行。
表1、不同催化剂的分散度和不同温度下氯化氢转化率
表2、不同催化剂的运行500h后氯化氢转化率
由表1、表2可见，本申请制备的催化剂在催化氯化氢氧化制氯气的整体活性明显优于对照组催化剂，尤其活性组分的分散度要远大于对照组，说明本申请制备的催化剂活性组分具有高分散度，因而表现出更加优异的活性，同时低含量的金属负载对成本降低具有重要意义。
实施例2-1
取金红石型二氧化钛30克，β相碳化硅70克，田菁粉2.0克，捏合均匀。加入30g的水后捏合40min，挤出成型得到直径3mm条形物，于空气中60℃干燥12小时，得干燥后的条形载体，将载体截成长度在5mm左右。
将干燥后的载体于空气中400℃干焙烧6小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含0.15克Ru的RuCl3·3H2O溶液加入0.15g的吐温-80配成25毫升进行浸渍，并于60℃干燥12小时，得干燥后的催化剂。
将干燥后的催化剂于空气中250℃干煅烧6小时，将产品用水洗，80℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+SiC)]*100＝0.39％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+SiC)]*100＝0.3％
最终得到催化剂强度120N/cm，比表面积为30m2/g，平均孔径0.02um，350℃下测 试导热系数为1.60W/m·℃。
实施例2-2
取金红石型二氧化钛45克，β相碳化硅55克，田菁粉5.0克，捏合均匀。加入25g的水后捏合40min，挤出成型得到直径3mm条形物，于空气中60℃干燥12小时，得干燥后的条形载体，将载体截成长度在5mm左右。
将干燥后的载体于空气中500℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含0.25克Ru的RuCl3·3H2O溶液加入0.5g的吐温-80配成25毫升进行浸渍，并于80℃干燥6小时，得干燥后的催化剂；
将干燥后的催化剂于空气中280℃干焙烧5小时；将产品用水洗，90℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+SiC)]*100＝0.65％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+SiC)]*100＝0.5％
最终得到催化剂强度130N/cm，比表面积为25m2/g，平均孔径0.04um，350℃下测试导热系数为1.21W/m·℃。
实施例2-3
取金红石型二氧化钛33克，β相氮化硅67克，羟乙基纤维素5.0克，混合均匀；称28g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中90℃干燥8小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中550℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含0.76克Ru的RuCl3·3H2O溶液加入2.0g的OP-10配成25毫升进行浸渍，并于80℃干燥10小时，得干燥后的催化剂。
将干燥后的催化剂于空气中300℃干煅烧4小时；将产品用水洗，100℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+Si3N4)]*100＝1.97％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+Si3N4)]*100＝1.5％
最终得到催化剂强度138N/cm，比表面积为28m2/g，平均孔径0.06um，350℃下测试导热系数为1.48W/m·℃。
实施例2-4
取金红石型二氧化钛45克，β相氮化硅55克，甲基纤维素4.0克，混合均匀；称35g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中100℃干燥5小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中650℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含1.56克Ru的RuCl3·3H2O溶液加入6.0g的吐温-80配成30毫升进行浸渍，并于80℃干燥10小时，得干燥后的催化剂。
将干燥后的催化剂于空气中400℃干煅烧2小时；将产品用水洗，110℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+Si3N4)]*100＝3.95％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+Si3N4)]*100＝3.0％
最终得到催化剂强度142N/cm，比表面积为50m2/g，平均孔径0.1um，350℃下测试导热系数为1.32W/m·℃。
实施例2-5
取金红石型二氧化钛40克，六方氮化硼60g、羟丙基甲基纤维素4.0克，混合均匀；称28g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中120℃干燥5小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中700℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含2.11克Ru的亚硝酰基硝酸钌溶液加入4.0g的PEG-400配成30毫升进行浸渍，并于100℃干燥7小时，得干燥后的催化剂。
将干燥后的催化剂于空气中350℃干煅烧4小时即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+BN)]*100＝5.2％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+BN)]*100＝4.0％
最终得到催化剂强度118N/cm，比表面积为26m2/g，平均孔径0.07um，350℃下测试导热系数为1.29W/m·℃。
实施例2-6
取金红石型二氧化钛50克，六方氮化硼50克，聚乙烯醇4.0克，混合均匀；称29g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中110℃干燥5小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中750℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含1.56克Ru的亚硝酰基硝酸钌溶液加入7.5g的PEG-400配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中500℃干煅烧2小时即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+BN)]*100＝3.95％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+BN)]*100＝3.0％
最终得到催化剂强度150N/cm，比表面积为22m2/g，平均孔径3um，350℃下测试导热系数为1.20W/m·℃。
实施例2-7
取金红石型二氧化钛60克，β相氮化硅40克，淀粉5.0克，混合均匀；称25g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中110℃干燥5小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中800℃干焙烧3小时，得焙烧后的条形载体,强度200N/cm，比表面积为34m2/g，平均孔径6um。
取焙烧后的载体50克，用含0.51克Ru的K2RuCl6溶液加入2.5g的吐温-80配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中550℃干煅烧5小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+Si3N4)]*100＝1.3％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+Si3N4)]*100＝1.0％
最终得到催化剂强度200N/cm，比表面积为18m2/g，平均孔径6um，350℃下测试导热系数为1.22W/m·℃。
实施例2-8
取金红石型二氧化钛50克，六方氮化硼50克，羟乙基纤维素3.0克，混合均匀；称25g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中110℃干燥5小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中600℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含0.25克Ru的[Ru(NH3)6]Cl2溶液加入0.5g的PEG-400 配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中400℃干煅烧3小时即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+BN)]*100＝0.66％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+BN)]*100＝0.5％
最终得到催化剂强度143N/cm，比表面积为24m2/g，平均孔径1.0um，350℃下测试导热系数为1.23W/m·℃。
实施例2-9
取金红石型二氧化钛35克，β相碳化硅65克，田菁粉10.0克，混合均匀；称30g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中110℃干燥5小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中650℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含0.92克Ru的RuBr3·3H2O溶液加入2.7g的OP-10配成30毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中350℃干煅烧2小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+SiC)]*100＝2.37％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+SiC)]*100＝1.8％
最终得到催化剂强度129N/cm，比表面积为20m2/g，平均孔径0.6um，350℃下测试导热系数为1.45W/m·℃。
实施例2-10
取金红石型二氧化钛60克，β相碳化硅40克，田菁粉8.0克，混合均匀；称26g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中110℃干燥5小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中650℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含0.4克Ru的RuCl3·3H2O溶液加入0.8g的PEG-400配成32毫升进行浸渍，并于110℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中300℃干煅烧3小时；将产品用水洗至无氯离子，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+Si3N4)]*100＝1.0％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+Si3N4)]*100＝0.8％
最终得到催化剂强度121N/cm，比表面积为27m2/g，平均孔径0.09um，350℃下测试导热系数为1.28W/m·℃。
实施例2-11
取金红石型二氧化钛55克，β相氮化硅45克，田菁粉3.0克，混合均匀；称28g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中120℃干燥4小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中750℃干焙烧4小时，得焙烧后的条形载体。
取焙烧后的载体50克，用含0.61克Ru的RuCl3·3H2O溶液加入1.8g的OP-10配成28毫升进行浸渍，并于120℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中350℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+Si3N4)]*100＝1.58％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+Si3N4)]*100＝1.2％
最终得到催化剂强度139N/cm，比表面积为42m2/g，平均孔径0.04um，350℃下测试导热系数为1.22W/m·℃。
实施例2-12
取金红石型二氧化钛30克，六方氮化硼60克，田菁粉3.0克，混合均匀；称30g的水倒入混合料中，进行捏合40min，挤出成型得到直径3mm条形物，于空气中120℃干燥4小时，得干燥后的条形载体，截成长度5mm；
将干燥后的载体于空气中600℃干焙烧4小时，得焙烧后的条形载体,强度153N/cm，比表面积为25m2/g，平均孔径0.9um。
取焙烧后的载体50克，用含1.03克Ru的RuCl3·3H2O溶液加入1.0g的PEG-400配成28毫升浸渍，并于120℃干燥6小时，得干燥后的催化剂。
将干燥后的催化剂于空气中280℃干煅烧3小时；将产品用水洗，120℃烘干即得催化剂产品。
理论计算得到催化剂组分质量百分含量为：
[RuO2/(RuO2+TiO2+BN)]*100＝2.63％
其中金属钌质量百分含量为：
[Ru/(RuO2+TiO2+BN)]*100＝2.0％
最终得到催化剂强度151N/cm，比表面积为25m2/g，平均孔径0.03um，350℃下测试导热系数为1.52W/m·℃。
对照组2-1
本实施例基于住友化学专利CN1272238C实施例18公开的技术方案制备负载氧化钌催化剂：
将市售的氧化钌水合物(RuCl3·nH2O，Ru含量37.3wt％)2.03克溶解于14.6g纯水中，搅拌后得至氯化钌水溶液。将所得的水溶液滴加到50.0克由氧化钛-α-氧化铝(氧化钛占比50％)组成的条形复合载体上，浸渍氯化钌。将载持的物质在空气中，60℃干燥2小时，得到氧化钛-α-氧化铝载持氯化钌。将所得的氧化钛-α-氧化铝载持氯化钌，在室温下加入由2mol/L的氢氧化钾水溶液10.5克和纯水300克以及水合肼2.54g组成的混合溶液，每15分钟搅拌一次，浸渍1h。在浸渍时可观察到溶液中发泡。直到发泡消失为止静置约15min后，过滤后注加0.5L纯水并搅拌后静置30分钟，然后过滤，如此重复5次。此后通过倾滤除去上清液。然后再加入调整至0.5mol/L的氯化钾水溶液100g加搅拌后静置30分钟，以倾滤除去上清液。将此操作重复3次。接着将洗涤的物质在空气中，60℃干澡4h得至含氯化钾的灰色球状固体。
然后，将得到的固体在空气中大约经l小时从室温升至350℃，并在该温度烧成3小时得到球状固体。在得到的固体中加入0.5L的纯水搅拌后放置30min并通过过滤进行水洗。重复进行5次该操作。水洗时间大约为4小时。将水洗的物质在空气中60℃干燥4h得到50.0克灰黑色负载氧化钌催化剂。
金属钌含量的计算值是1.5％Ru/(TiO2:Al2O3＝50:50)，350℃下测试导热系数为0.57W/m·℃。
试验例2-1
所有实施例催化剂的活性在固定床催化反应器上进行；反应器类型：石英管管式反应器，内径25mm；催化剂粒度为原颗粒，用量为10g；主要反应条件为：0.1Mpa，HCl以0.76L/min，O2以0.64L/min通过催化剂床层。不同温度下转化率见表3和表4，实施例2-1至实施例2-12与对照组2-1在相近条件下进行：
表3、不同实施例催化剂的热导率和不同温度下氯化氢转化率
表4、不同实施例催化剂的运行500h后转化率
由表3、4可见，实施例2-1至实施例2-12制备的催化剂整体活性均高于对照组， 特别是高温区间的转化率和高温下催化剂的寿命显著提高。
以上所述仅是本申请的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。

Claims (10)

  1. 一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于包括：
    (1)将含钌活性组分通过表面活性剂分散制成浸渍液，(2)将所述浸渍液接触附着于氧化钛和氧化铝的复合载体上，干燥后煅烧，(3)冷却、水洗，烘干，
    或(1)将氧化钛、高导热陶瓷和助剂混合以获得混合粉体，所述混合粉体与水混合，成型、烘干，经第一次煅烧获得高强度载体，其中高导热陶瓷选自Si3N4、BN、SiC中的任意一种或多种，(2)将钌活性组分前驱体溶液制备成浸渍液，所述浸渍液中还包括表面活性剂，(3)将所述浸渍液浸渍于高强度载体上，烘干，经第二次煅烧后获得所述钌催化剂；
    其中，所述表面活性剂选自聚氧乙烯型非离子表面活性剂、聚乙二醇、聚山梨酯的任意一种或多种，表面活性剂的用量为所述含钌活性组分中金属元素质量的1-10倍，钌催化剂具有比表面积为10-50m2/g，钌元素占所述钌催化剂的0.1-10wt％。
  2. 根据权利要求1所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：所述表面活性剂选自T-80、OP-10、PEG-400中的任意一种或多种；
    和/或所述钌活性组分选自三氯化钌或其水合物、三溴化钌或其水合物、氯钌酸盐或其水合物、钌酸盐、氯氧化钌、氯氧化钌盐、钌氨配合物、氯化钌胺络合物、溴化钌胺络合物、乙酰丙酮钌、羰基钌、钌的有机酸盐、亚硝酰基硝酸钌、钌-亚硝酰基配合物、钌磷配合物的任意一种或多种的组合；
    和/或所述助剂选自聚乙烯醇、纤维素、淀粉、田菁粉、合成树脂的任意一种或多种；助剂为混合粉体的1-10wt％；
    和/或氧化钛为金红石型二氧化钛；
    和/或氧化铝为α-Al2O3。
  3. 根据权利要求1所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：所述浸渍液接触附着中的浸渍方式为等体积浸渍、过量浸渍、喷洒浸渍的任意一种；和/或浸渍液接触附着于30-60℃温度下完成；和/或干燥后煅烧中的煅烧温度为150-700℃，时间为1-24小时。
  4. 根据权利要求1所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：所述复合载体通过成型工艺制备获得的形状包括粉末状、球形、柱状、异型、蜂窝状的任意一种或多种。
  5. 根据权利要求1所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：钌元素占所述钌催化剂的0.3-5wt％。
  6. 根据权利要求1所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：钌晶粒粒径在1-10nm，金属钌表面积为120-410m2/(g·Ru)。
  7. 根据权利要求1所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：钌催化剂的孔径为0.01-6um，直径为1.5-3mm圆柱时强度为120-200N/cm。
  8. 根据权利要求1所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：所述第一次煅烧是在300-800℃内煅烧1-24h；和/或所述第二次煅烧是在200-700℃内煅烧1-24h，然后自然冷却至室温。
  9. 根据权利要求7所述的一种用于氯化氢氧化制氯气的高分散度钌催化剂的制备方法，其特征在于：所述钌催化剂基于热线法在350℃时的导热率为0.6-2.0W/m·℃。
  10. 一种钌催化剂，其特征在于：所述钌催化剂由权利要求1-9任一项所述的方法制备获得。
PCT/CN2024/094092 2023-05-22 2024-05-18 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 Pending WO2024240099A1 (zh)

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