CN117839688A - Preparation method and application of supported ruthenium-based catalyst - Google Patents
Preparation method and application of supported ruthenium-based catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- -1 fluoride ions Chemical class 0.000 claims abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000004334 fluoridation Methods 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 4
- 238000005470 impregnation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229940052810 complex b Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a supported ruthenium-based catalyst. The disclosed scheme is that fluoride ion-containing aqueous solution is adopted to carry out fluoridation treatment on an oxide carrier; loading ruthenium component on the carrier after fluorination treatment; then adopting an alcohol aqueous solution to carry out solvothermal treatment on the solid compound; finally roasting to obtain the supported ruthenium-based catalyst. According to the invention, the oxide carrier is subjected to fluorination treatment, so that defects on the surface of the carrier can be increased, and meanwhile, fluoride ions participate in regulating and controlling the electronic structure of ruthenium sites on the surface, which is beneficial to anchoring ruthenium components and limiting migration and sintering of the ruthenium components under heat treatment or high-temperature reaction atmosphere; on the basis, the solvothermal treatment is carried out by adopting an aqueous solution of alcohol, so that the fixed ruthenium component is further reconstructed and the electronic structure is optimized. The catalyst of the invention can be used as a catalyst for preparing chlorine by circulating hydrogen chloride, and the stability and activity of the catalyst are obviously improved.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a supported ruthenium-based catalyst.
Background
In many chemical processes, over 50% of the chemical reactions involve elemental chlorine, with chlorine and hydrogen chloride being the most common. The chlorine industry comprises a plurality of fields of polyurethane, fluoride, chlor-alkali, medicine, electronics, cosmetics and the like, and has become an essential component of modern industrial civilization. However, due to the wide industrial application of chlorine, a large amount of hydrogen chloride by-product is inevitably produced. In order to realize the high-quality development of the chlorine industry, the resource efficient utilization of byproduct hydrogen chloride has become a key problem to be solved urgently.
The hydrogen chloride is converted into chlorine again, so that the recycling of chlorine resources can be realized, and the method is a green way for promoting the sustainable development of chlorine industry. The catalytic oxidation method is the most efficient method for preparing chlorine by circulating hydrogen chloride, but the current mainstream ruthenium-based catalyst still has the problem of long-period stability, and ruthenium components can migrate and sinter in the high-temperature reaction process, so that the activity is gradually reduced.
Disclosure of Invention
Aiming at the defects or deficiencies of the stability and activity of the ruthenium-based catalyst in the prior art, the invention provides a preparation method of a supported ruthenium-based catalyst.
Therefore, the preparation method of the supported ruthenium-based catalyst provided by the invention comprises the following steps:
(1) Carrying out fluorination treatment on the oxide carrier by using a fluoride ion-containing aqueous solution to obtain a fluorination treatment carrier; the oxide carrier is one or more than two of rutile titanium dioxide, anatase titanium dioxide, tin dioxide, gamma-alumina and alpha-alumina;
(2) Ru element is loaded on the fluoridation treatment carrier, and then a solid compound is obtained after first roasting;
(3) And (3) carrying out heat treatment on the solid compound in an aqueous solution of alcohol under a sealing condition, and then preparing the supported ruthenium-based catalyst through second roasting.
Alternatively, the fluorine-containing ion aqueous solution is fluoride HF, NH 4 F. An aqueous solution of one or more of NaF, KF and CsF.
Alternatively, the mass fraction of the fluoride ions in the fluoride ion-containing aqueous solution is 0.1-5.0%.
Alternatively, the mass ratio of the fluorine-containing ion aqueous solution to the oxide carrier is 100:1-60.
Alternatively, the Ru element loading in the step (2) is performed by an immersion method or an alkali precipitation method.
Alternatively, the first roasting temperature is 150-400 ℃ and the roasting time is 0.5-10 h.
Alternatively, the aqueous solution of the alcohol in the step (3) is one or more aqueous solutions of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol and glycerol.
Alternatively, the mass ratio of the alcohol to the water in the aqueous solution of the alcohol in the step (3) is 100:20-600.
Alternatively, the mass ratio of the aqueous solution of the alcohol to the solid composite in the step (3) is 100:1-80.
Alternatively, the heat treatment temperature in the step (3) is 30-200 ℃, and the treatment time is 0.5-10 h.
The alternative proposal is that the second roasting temperature in the step (3) is 140-300 ℃ and the roasting time is 0.5-8 h.
12. A method for preparing chlorine, which is characterized in that the catalyst adopted in the method is the catalyst as claimed in claim 1.
In the supported ruthenium-based catalyst, the defects on the surface of the carrier can be increased by carrying out fluorination treatment on the oxide carrier, and meanwhile, fluoride ions participate in regulating and controlling the electronic structure of ruthenium sites on the surface, so that the supported ruthenium-based catalyst is beneficial to anchoring ruthenium components and limiting migration and sintering of the supported ruthenium components under the heat treatment or high-temperature reaction atmosphere; and then adopting alcohol-water solution to make solvothermal treatment so as to promote further reconstruction of fixed ruthenium component and optimize electronic structure. The preparation method of the invention can obviously improve the stability and activity of the supported ruthenium-based catalyst. The catalyst of the invention is particularly suitable for being used as a catalyst in preparing chlorine by catalytic oxidation of hydrogen chloride.
Detailed Description
Unless specifically stated otherwise, the terms herein are to be understood based on knowledge of one of ordinary skill in the relevant art. It should also be understood that the temperatures, durations referred to herein are approximations for purposes of illustration. Although methods and materials similar or equivalent to those described herein can be used in the practice of the present disclosure, some suitable methods and materials are described below. In addition, the materials, methods, material ratios, and example embodiments are illustrative only and not intended to be limiting. In a specific scheme, a person skilled in the art can optimize the material proportion and the operation parameter value involved in the method according to the disclosure of the invention by adopting a conventional experimental period to achieve the aim of the invention.
In the present invention, the ruthenium element may be supplied as ruthenium salt such as ruthenium trichloride, ruthenium trichloride hydrate, or ruthenium acetylacetonate.
Elemental content analysis of the catalysts in the examples below was determined using inductively coupled plasma atomic emission spectrometry.
Example 1:
3.12g of rutile TiO 2 And 1.03g of anatase TiO 2 After fully mixing, adding the mixture into 20.21g of HF aqueous solution (HF content is 0.8 wt%) and magnetically stirring the mixture for 2.0h at a rotating speed of 100r/min, filtering the mixture, washing filter residues with deionized water for 3 times, and drying the filter residues at 100+/-10 ℃ for 4.0h to obtain 3.82g of fluorinated carrier A;
0.16g RuCl 3 ·3H 2 O is dissolved in 50mL of deionized water; then adding 2.03g of the fluoridized carrier A, and strongly stirring and impregnating for 16 hours; evaporating the solvent from the obtained material at 50+/-5 ℃ under vacuum, drying at 80 ℃ for 3 hours, and roasting at 350+/-10 ℃ for 4 hours to obtain 2.01g of solid compound A;
adding 2.01g of solid compound A into an aqueous solution of alcohol prepared by fully mixing 6.56g of ethanol, 12.35g of ethylene glycol and 8.82g of deionized water, stirring and uniformly mixing, transferring the solid-liquid mixture into a tetrafluoro lining of a stainless steel autoclave, sealing the autoclave, placing the autoclave in a heating furnace, performing solvothermal treatment at 120+/-10 ℃ for 4 hours, then washing the autoclave for 3 times by cooling, filtering, deionized water and ethanol, drying at 80+/-5 ℃ for 4 hours, and roasting at 150+/-10 ℃ for 3 hours to obtain 1.97g of supported ruthenium-based catalyst A, wherein the mass content of Ru element in the catalyst is 2.96%.
Example 2:
3.57g of rutile TiO 2 、1.01g SnO 2 And 0.65g of alpha-alumina are fully mixed, added into 27.86g of HF aqueous solution (HF content is 0.72 wt%) and magnetically stirred for 2.5h at a rotating speed of 120r/min, filtered and washed with deionized water for 3 times, and dried for 5.0h at 100+/-10 ℃ to obtain 5.02g of fluoridized carrier B;
0.16g RuCl 3 ·3H 2 O is dissolved in 50mL of deionized water; then adding 2.01g of the fluoridized carrier B, and strongly stirring and dipping for 16h; the resulting material was then evaporated to dryness under vacuum at 50.+ -. 5 ℃ for 3h at 80.+ -. 5 ℃ and calcined at 350.+ -. 10 ℃ for 4h to give 2.02g of solid complex B.
2.02g of solid compound B is added into an alcohol-water solution which is prepared by fully mixing 10.96g of methanol, 4.63g of glycerol and 11.31g of deionized water, the mixture is fully stirred for 10min, the solid-liquid mixture is transferred into a tetrafluoro lining of a stainless steel autoclave, the autoclave is sealed and then placed into a heating furnace for solvothermal treatment at 100+/-10 ℃ for 3h, and then the autoclave is cooled, filtered, washed with deionized water and methanol for 3 times and dried at 80+/-5 ℃ for 4h, and baked at 180+/-10 ℃ for 2h to obtain 1.94g of supported ruthenium-based catalyst B, wherein the mass content of Ru element in the catalyst is 2.99%.
Comparative example 1:
0.16g RuCl 3 ·3H 2 O is dissolved in 50mL of deionized water; then 1.52g of rutile TiO was added 2 And 0.50g of anatase TiO 2 Stirring and soaking for 16h; and evaporating the solvent from the obtained material at 50+/-5 ℃ under vacuum, drying for 3 hours at 80+/-5 ℃ and roasting for 4 hours at 350+/-10 ℃ to obtain 2.01g of supported ruthenium-based catalyst C, wherein the mass content of Ru element in the catalyst is 3.01%.
Comparative example 2:
0.16g RuCl 3 ·3H 2 O is dissolved in 50mL of deionized water; then 1.37g of rutile TiO was added 2 、0.39g SnO 2 And 0.25g of alpha-alumina, with vigorous stirring, for 16h; and evaporating the solvent from the obtained material at 50+/-5 ℃ under vacuum, drying for 3 hours at 80+/-5 ℃ and roasting for 4 hours at 350+/-10 ℃ to obtain 1.93g of supported ruthenium-based catalyst D, wherein the mass content of Ru element in the catalyst is 3.04%.
Catalyst evaluation:
the catalyst is evaluated by adopting a fixed bed reactor, the reactor size is 350mm multiplied by phi 10mm multiplied by 1mm, the reaction is carried out under normal pressure, 1.50g of catalyst is filled, the particle size of the catalyst is 0.1-0.18mm, hydrogen chloride gas and oxygen are taken as reaction gases, and the reaction gases firstly pass through a mass flowmeter and then enter the fixed bed reactor after passing through a preheater;
the fixed bed reactor adopts three-stage heating in an electric heating mode, the reaction temperature is 350+/-10 ℃, the hydrogen chloride flow is 80ml/min, the oxygen flow is 160ml/min, namely the reaction airspeed is 9600L/(kg) cat ·h)；
After the reaction is stabilized for 1h, sampling and analyzing are carried out, and respectively titrating chlorine in the sample and hydrogen chloride which is not completely reacted by adopting an iodometry method and an acid-base titration method. The specific operation steps are as follows: after the system is stable in operation, 100mL of 20% KI solution is prepared at regular intervals, a three-way valve at the outlet of an oxidation reactor is switched, the mixed gas after reaction is introduced into a constant-volume (100 mL) potassium iodide solution for 2 minutes, the absorption liquid is moved into a conical flask after absorption, and 0.1mol/L sodium thiosulfate standard solution is used for titration, and starch is used as an indicator; unreacted HC1 was then titrated with 0.1mol/L sodium hydroxide standard solution using phenolphthalein as an indicator.
The catalysts obtained in examples 1 and 2 and comparative examples 1 and 2 were evaluated by a fixed bed reactor under the above high space velocity reaction conditions, and the hydrogen chloride catalytic oxidation performance was shown in Table 1 below, in which the catalyst stability was expressed as Cl at 100 hours of reaction 2 The space-time yield is Cl at 1h of reaction 2 Percentage of space-time yield.
TABLE 1
As can be seen from Table 1, the catalytic activity and stability of the hydrogen chloride oxidation catalyst A, B obtained by the preparation method of the invention are higher than those of the catalyst C, D prepared by the conventional method under the condition that the Ru content in the catalyst is the same or basically the same. The method plays a remarkable role in gain for improving the performance, especially stability, of the supported ruthenium-based catalyst. For example, the above example shows that 9600L/(kg) at high airspeed cat And h) using the catalyst of the invention to continuously react for 100 hours, wherein the catalytic activity is not basically attenuated.
Claims (12)
1. A method for preparing a supported ruthenium-based catalyst, the method comprising:
(1) Carrying out fluorination treatment on the oxide carrier by using a fluoride ion-containing aqueous solution to obtain a fluorination treatment carrier; the oxide carrier is one or more than two of rutile titanium dioxide, anatase titanium dioxide, tin dioxide, gamma-alumina and alpha-alumina;
(2) Ru element is loaded on the fluoridation treatment carrier, and then a solid compound is obtained after first roasting;
(3) And (3) carrying out heat treatment on the solid compound in an aqueous solution of alcohol under a sealing condition, and then preparing the supported ruthenium-based catalyst through second roasting.
2. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the aqueous solution containing fluoride ions is fluoride HF, NH 4 F. An aqueous solution of one or more of NaF, KF and CsF.
3. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the mass fraction of fluoride ions in the aqueous solution containing fluoride ions is 0.1 to 5.0%.
4. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the mass ratio of the fluorine-containing ion aqueous solution to the oxide support is 100:1 to 60.
5. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the Ru element loading in the step (2) is performed by an impregnation method or an alkali precipitation method.
6. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the first firing temperature is 150 to 400 ℃ and the firing time is 0.5 to 10 hours.
7. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the aqueous solution of alcohol in the step (3) is an aqueous solution of one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol and glycerol.
8. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the mass ratio of the alcohol to water in the aqueous solution of the alcohol in the step (3) is 100:20-600.
9. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the mass ratio of the aqueous solution of the alcohol to the solid composite in the step (3) is 100:1 to 80.
10. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the heat treatment temperature in the step (3) is 30 to 200 ℃ and the treatment time period is 0.5 to 10 hours.
11. The method for preparing a supported ruthenium-based catalyst according to claim 1, wherein the second firing temperature in the step (3) is 140 to 300 ℃ and the firing time is 0.5 to 8 hours.
12. A method for preparing chlorine by catalytic oxidation of hydrogen chloride, which is characterized in that the catalyst adopted in the method is the catalyst of claim 1.
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