CN107952432B - Preparation method of hydrogen chloride oxidation catalyst - Google Patents
Preparation method of hydrogen chloride oxidation catalyst Download PDFInfo
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- CN107952432B CN107952432B CN201711220899.8A CN201711220899A CN107952432B CN 107952432 B CN107952432 B CN 107952432B CN 201711220899 A CN201711220899 A CN 201711220899A CN 107952432 B CN107952432 B CN 107952432B
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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
- B01J23/462—Ruthenium
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
Abstract
The invention provides a preparation method of a hydrogen chloride oxidation catalyst, which comprises the following steps: adding the powder carrier into the ruthenium precursor aqueous solution, dropwise adding a hydrogen peroxide solution after fully stirring, uniformly mixing, heating, then adjusting the pH value of the solution by using alkali, then carrying out solid-liquid separation treatment, and drying the solid obtained by separation to obtain the hydrogen chloride oxidation catalyst. The hydrogen chloride oxidation catalyst prepared by the invention can overcome the defects of high energy consumption, large water consumption, complicated steps, difficult industrial amplification preparation, low utilization efficiency of noble metal ruthenium and the like of the existing hydrogen chloride oxidation catalyst preparation method, and has the advantages of few process steps, low water consumption, low energy consumption, short period and high yield.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a hydrogen chloride oxidation catalyst.
Background
Preparation of chlorine gas (2HCl (g) + 1/2O) by catalytic oxidation of hydrogen chloride2→H2O+Cl2) Also known as the Deacon process, was proposed by Henry Deacon in 1868. The Deacon process can convert industrial byproduct hydrogen chloride into chlorine, realizes cyclic utilization of chlorine resources, and is the most effective, economic and environment-friendly method for solving the problems of hydrogen chloride discharge and recycling. The Deacon reaction is exothermic and the equilibrium conversion decreases with increasing reaction temperature, so the catalyst must have very good low temperature activity. Among the numerous catalysts having hydrogen chloride oxidation activity, supported ruthenium catalysts are the best catalyst systems having low temperature activity. It is well known that the preparation method of the catalyst affects not only the catalytic performance but also the cost of the industrial catalyst.
The catalyst prepared by the impregnation method is difficult to control the size of active component particles, so that the dispersibility of the active component is poor, and the activity of the catalyst is reduced. Ru/SiO for hydrogen chloride oxidation is described in GB10463132Catalyst with RuCl3Loading the precursor to SiO by an isometric impregnation method2A carrier surface. CN101663092 discloses ruthenium catalysts containing different promoters, and the preparation method also adopts an impregnation method, although the promoters can improve the stability of the catalyst, the preparation method leads to RuO2The problem of poor dispersibility remains unsolved. CN12457738 reports some ruthenium catalysts for hydrogen chloride oxidation, wherein an excess impregnation method is adopted in some examples, however, the excess impregnation method requires evaporation of excess solvent, which not only increases energy consumption, but also reduces the dispersibility of active components due to the change of the concentration of the impregnation solution during evaporation.
Precipitation deposition and coprecipitation methods are also used for the preparation of hydrogen chloride oxidation catalysts. CN1145328 reports a ruthenium catalyst for hydrogen chloride oxidation prepared by reacting RuCl3After the solution is precipitated with alkali, it is mixed with a freshly prepared carrier to complete the loading process. CN101448735 reports a supported ruthenium catalyst, the carrier is rutile crystal type stannic oxide, and the preparation method is a precipitation deposition method, namely ruthenium halide is precipitated to SnO through alkali2A surface. CN101722019 adopts a precipitation deposition method to prepare a catalyst containing a magnesium fluoride carrier supported ruthenium compound. In the CN1145328 example, part of the catalysts adopt a coprecipitation method, that is, a carrier precursor and an active component precursor form a precipitate together, and then the catalyst is prepared by post-treatment. The salt generated by precipitating solution and post-cleaning in the preparation process of the precipitation deposition method needs a large amount of water, more water resources are consumed, and the catalyst prepared by the method is not easy to amplify and has higher preparation cost. The coprecipitation method has the above disadvantages of the precipitation deposition method, and is not suitable for the preparation of noble metal catalysts because the coprecipitation causes the embedding of the active component, which reduces the utilization rate of the active component.
In view of the above disadvantages of the conventional catalyst preparation method, the ruthenium catalyst reported in CN1245773 adopts an improved hydrogen chlorideA method for preparing a catalyst. On the basis of the traditional impregnation method, the activity of the catalyst is improved by reduction treatment under alkaline conditions and treatment of alkali metal chloride. However, this method includes complicated steps such as loading, alkali treatment, reduction, washing, alkali chloride treatment, drying, calcination, washing, and drying, and is not suitable for industrial scale-up production. The literature reports a high-dispersity nano RuO for hydrogen chloride oxidation2/TiO2Catalyst (catal. sci. technol.,2013,3,2555), first a nano RuO was synthesized by a nano preparation method2The solution is then prepared by excess impregnation of the support and rotary evaporation of the excess solution. However, the typical nano-synthesis method for preparing industrial catalysts has many disadvantages which are difficult to overcome, for example, the protective agent added in the process of synthesizing the nano-particles needs to be post-treated, the amount of the solvent is large, the yield is low, and the process of loading the nano-particles needs to rotate and evaporate excessive solvent, which not only increases the energy consumption, but also makes it difficult to prepare the catalyst with large loading capacity. Therefore, the nano preparation method has the advantages of high cost, low yield, multiple steps and difficult industrial amplification.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a hydrogen chloride oxidation catalyst, which can solve the disadvantages of high energy consumption, large water consumption, complicated steps, difficult industrial scale-up preparation, low utilization efficiency of noble metal ruthenium, etc. of the existing method for preparing the hydrogen chloride oxidation catalyst.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a hydrogen chloride oxidation catalyst is characterized by comprising the following steps: firstly, respectively weighing a ruthenium precursor aqueous solution, a hydrogen peroxide solution and a powder carrier according to the molar ratio of (0.3-3) to (0.5-10) to 100 of the ruthenium precursor, then adding the powder carrier into the ruthenium precursor aqueous solution, dropwise adding the hydrogen peroxide solution after fully stirring, uniformly mixing, heating to 80-100 ℃, preserving the temperature for 1-10 h, then adjusting the pH value of the solution to 6-12 by using alkali, finally performing solid-liquid separation treatment, and drying the separated solid to obtain the hydrogen chloride oxidation catalyst.
The preparation method of the hydrogen chloride oxidation catalyst is characterized in that the ruthenium precursor is anhydrous ruthenium trichloride or hydrated ruthenium trichloride; the mass concentration of ruthenium in the ruthenium precursor aqueous solution is 0.1-5%. According to the research of the invention, if the mass concentration of Ru (III) is less than 0.1%, the consumed water amount is too large, and the cost of the catalyst is increased; if the mass concentration of Ru (III) is more than 5%, RuO will be reduced2Degree of dispersion on the surface of the support. Therefore, the mass concentration of Ru (III) is preferably 0.1 to 5%, more preferably 0.2 to 2%.
The preparation method of the hydrogen chloride oxidation catalyst is characterized in that the mass concentration of the hydrogen peroxide solution is 10-50%. The research of the invention finds that if the concentration of the hydrogen peroxide is less than 10 percent, the consumed water amount is overlarge, and the cost of the catalyst is increased; if the concentration of the hydrogen peroxide is more than 50%, the price of the hydrogen peroxide is obviously increased, and the cost of the catalyst is increased. Therefore, the concentration of the hydrogen peroxide is suitable to be 10-50%, and more preferably 20-30%.
The preparation method of the hydrogen chloride oxidation catalyst is characterized in that the powder carrier is a compound formed by at least one of lanthanum oxide, cerium dioxide, aluminum oxide, silicon dioxide, nickel oxide and cobaltosic oxide and titanium dioxide, or titanium dioxide or/and tin dioxide.
The preparation method of the hydrogen chloride oxidation catalyst is characterized in that the alkali is any one or more than two of water glass, sodium metasilicate and sodium metaaluminate.
The preparation method of the hydrogen chloride oxidation catalyst is characterized in that the active component in the hydrogen chloride oxidation catalyst is ruthenium dioxide, and the mass ratio of the ruthenium dioxide to the carrier is (0.1-1): 20. In the invention, if the loading amount of ruthenium dioxide relative to the carrier is more than 5 percent, the utilization rate of noble metal is reduced, and the cost of the catalyst is increased; if the loading of ruthenium dioxide with respect to the support is less than 0.5%, the activity per unit mass of the catalyst is low and does not meet the industrial requirements. Therefore, the amount of ruthenium dioxide supported on the carrier is suitably 0.5% to 5%.
In the invention, the adding sequence of the ruthenium precursor aqueous solution and the hydrogen peroxide aqueous solution can be changed, namely: and adding the powder carrier into a hydrogen peroxide solution, fully stirring, and then dropwise adding a ruthenium precursor aqueous solution. The products of the invention can likewise be produced.
In the invention, the solid isolate can be roasted (at the temperature of 250-450 ℃ for 2-10 h) to obtain a final product, or the solid isolate can be roasted to obtain the final product.
In the invention, the amount of chlorine generated at the outlet is titrated and analyzed by iodometry, and the conversion rate of HCl and the space-time yield of ruthenium in unit molar weight are calculated as follows:
wherein the unit of the chlorine generation rate at the outlet and the HCl gas inlet rate is mol/min.
Wherein the unit of the generation rate of the outlet chlorine gas is mol/min, and the unit of the molar quantity of Ru in 0.1g of the catalyst is mol.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method is suitable for preparing the industrial catalyst, and has the advantages of few steps, low water consumption, low energy consumption, short period and high yield;
(2) in the process of preparing the catalyst by adopting the method, the powder carrier is fully dispersed in the solution, the outer surface of the carrier can be fully utilized, and the loading capacity is improved;
(3) in the process of preparing the catalyst by adopting the method, when the loading capacity of the ruthenium dioxide is in the range of 0.5-5%, the ruthenium dioxide can be uniformly deposited on the surface of the carrier, so that the dispersibility of ruthenium dioxide particles is improved, and the utilization efficiency of noble metal ruthenium is increased;
(4) in the process of preparing the catalyst by adopting the method, the addition of the alkali not only enables the carrier powder to be separated by precipitation, but also enables the unreacted ruthenium precursor to be precipitated and deposited on the surface of the carrier, thereby improving the preparation yield of the catalyst.
(5) In the process of preparing the catalyst by adopting the method, the ruthenium dioxide active component can be obtained without roasting, and the defects of energy consumption and pollution in the traditional preparation method are overcome.
The present invention will be described in further detail with reference to examples.
Detailed Description
Example 1
This example provides a method for preparing a hydrogen chloride oxidation catalyst, comprising the steps of:
step one, 0.14g of commercially available RuCl3.nH2O (Ru mass content)>37%) into 50g of distilled water to obtain a solution with the ruthenium mass content of 0.1%, which is named as solution one;
adding 20g of commercially available 30% hydrogen peroxide into 20g of distilled water to obtain a solution with the hydrogen peroxide content of 15%, and naming the solution as solution II;
step three, adding a powder titanium dioxide carrier (rutile type, an avastin reagent) into the solution I according to the molar ratio of the ruthenium precursor to the hydrogen peroxide to the titanium dioxide of 0.3:0.5:100, and fully stirring to obtain a solution III; then dropwise adding the solution II into the solution III to obtain a solution IV;
step four, heating the solution four to 80 ℃, and keeping for 4 hours to obtain a solution five;
regulating the pH value of the solution to 6 by using sodium metasilicate, and then carrying out solid-liquid separation by adopting a filtering mode;
and step six, drying the solid material body obtained after the solid-liquid separation treatment in the step five at 60 ℃ to obtain a hydrogen chloride oxidation catalyst finished product.
The catalyst prepared in this example was designated as catalyst 1. The loading of ruthenium dioxide on the support in this catalyst was 0.5% based on the mass of the support.
Example 2
This example provides a method for preparing a hydrogen chloride oxidation catalyst, comprising the steps of:
step one, 0.68g of commercially available RuCl3.nH2O (Ru mass content)>37%) was added to 50g of distilled water to obtain a solution with a ruthenium content of 0.5% by mass, which was named solution one;
step two, adding 20g of distilled water into 20g of commercially available 50% hydrogen peroxide to obtain a solution with the hydrogen peroxide content of 25%, and naming the solution as solution two;
step three, adding a powder titanium dioxide carrier (rutile type, an avastin reagent) into the solution I according to the molar ratio of the ruthenium precursor to the hydrogen peroxide to the titanium dioxide of 0.6:2:100, and fully stirring to obtain a solution III; then dropwise adding the solution II into the solution III to obtain a solution IV;
step four, heating the solution four to 90 ℃, and keeping for 2 hours to obtain a solution five;
regulating the pH value of the solution to be more than 6 by using sodium metasilicate, and then carrying out solid-liquid separation by adopting a filtering mode;
and step six, drying the solid material body obtained after the solid-liquid separation treatment in the step five at 80 ℃ to obtain the hydrogen chloride oxidation catalyst finished product.
The catalyst prepared in this example was designated catalyst 2. The loading of ruthenium dioxide on the support in this catalyst was 1% based on the mass of the support.
Example 3
This example provides a method for preparing a hydrogen chloride oxidation catalyst, comprising the steps of:
step one, 7.81g of commercially available RuCl3.nH2O (Ru mass content)>37%) was added to 50g of distilled water to obtain a solution with a ruthenium content of 5% by mass, which was named solution one;
step two, a solution with 35% of hydrogen peroxide content is sold in the market and is named as solution two;
step three, adding a powder titanium dioxide carrier (rutile type, an Aladdin reagent) into the solution I according to the molar ratio of the ruthenium precursor, hydrogen peroxide and titanium dioxide of 3:10:100, and fully stirring to obtain a solution III; then dropwise adding the solution II into the solution III to obtain a solution IV;
step four, heating the solution four to 90 ℃, and keeping for 2 hours to obtain a solution five;
regulating the pH value of the solution to be more than 6 by using sodium metasilicate, and then carrying out solid-liquid separation by adopting a filtering mode;
and step six, drying the solid material body obtained after the solid-liquid separation treatment in the step five at 80 ℃ to obtain the hydrogen chloride oxidation catalyst finished product.
The catalyst prepared in this example was designated as catalyst 3. The loading of ruthenium dioxide on the support in this catalyst was 5% based on the mass of the support.
Example 4
This example provides a method for preparing a hydrogen chloride oxidation catalyst, comprising the steps of:
step one, 2.86g of commercially available RuCl3.nH2O (Ru mass content)>37%) was added to 50g of distilled water to obtain a solution with a ruthenium content of 2% by mass, which was named solution one;
step two, a solution with 35% of hydrogen peroxide content is sold in the market and is named as solution two;
step three, adding a powder titanium dioxide carrier (rutile type, an avastin reagent) into the solution two according to the molar ratio of the ruthenium precursor to the hydrogen peroxide to the titanium dioxide of 1.2:5:100, and fully stirring to obtain a solution three; adding the solution one drop by drop into the solution three to obtain a solution four;
step four, heating the solution four to 90 ℃, and keeping for 2 hours to obtain a solution five;
regulating the pH value of the solution to be more than 6 by using sodium metasilicate, and then carrying out solid-liquid separation by adopting a filtering mode;
and step six, drying the solid material body obtained after the solid-liquid separation treatment in the step five at 80 ℃, and then roasting at 250 ℃ for 4 hours to obtain the hydrogen chloride oxidation catalyst finished product.
The catalyst prepared in this example was designated catalyst 4. The loading of ruthenium dioxide on the support in this catalyst was 2% based on the mass of the support.
Example 5
This example provides a method for preparing a hydrogen chloride oxidation catalyst, comprising the steps of:
step one, 2.86g of commercially available RuCl3.nH2O (Ru mass content)>37%) was added to 50g of distilled water to obtain a solution with a ruthenium content of 2% by mass, which was named solution one;
step two, a solution with 35% of hydrogen peroxide content is sold in the market and is named as solution two;
step three, adding a powder tin dioxide carrier (a Chinese medicine reagent) into the solution II according to the molar ratio of the ruthenium precursor to the hydrogen peroxide to the tin dioxide of 1.13:5:100, and fully stirring to obtain a solution III; adding the solution one drop by drop into the solution three to obtain a solution four;
step four, heating the solution four to 100 ℃, and keeping for 2 hours to obtain a solution five;
step five, adjusting the pH value of the solution five to be more than 6 by using sodium metaaluminate, and then carrying out solid-liquid separation by adopting a filtering mode;
and step six, drying the solid material body obtained after the solid-liquid separation treatment in the step five at 80 ℃ to obtain the hydrogen chloride oxidation catalyst finished product.
The catalyst prepared in this example was designated catalyst 5. The loading of ruthenium dioxide on the support in this catalyst was 1% based on the mass of the support.
Example 6
This example provides a method for preparing a hydrogen chloride oxidation catalyst, comprising the steps of:
step one, 2.86g of commercially available RuCl3.nH2O (Ru mass content)>37%) was added to 50g of distilled water to obtain a solution with a ruthenium content of 2% by mass, which was named solution one;
step two, a solution with 35% of hydrogen peroxide content is sold in the market and is named as solution two;
step three, adding a powder tin dioxide carrier (a Chinese medicine reagent) into the solution II according to the molar ratio of the ruthenium precursor to the hydrogen peroxide to the tin dioxide of 2.26:5:100, and fully stirring to obtain a solution III; adding the solution one drop by drop into the solution three to obtain a solution four;
step four, heating the solution four to 90 ℃, and keeping for 2 hours to obtain a solution five;
regulating the pH value of the solution V to be more than 8 by using water glass, and then carrying out solid-liquid separation in a filtering mode;
and step six, drying the solid material body obtained after the solid-liquid separation treatment in the step five at 80 ℃ to obtain the hydrogen chloride oxidation catalyst finished product.
The catalyst prepared in this example was designated catalyst 6. The loading of ruthenium dioxide on the support in this catalyst was 2% based on the mass of the support.
Comparative example 1
The comparative example provides a preparation method of a hydrogen chloride oxidation catalyst, which comprises the following steps: first 0.82g of commercially available RuCl was added3.nH2O (Ru mass content)>37%) was added to 5.48g of distilled water to obtain a solution having a ruthenium content of 4.8% by mass. The solution was then immersed in an equal volume of 20g of powdered titanium dioxide carrier (rutile form, avadin reagent) and allowed to stand overnight. And then drying the impregnated solid at 100 ℃ for 10h, and roasting in a muffle furnace at 300 ℃ for 5h to obtain a finished catalyst.
The catalyst prepared in this comparative example was designated as comparative catalyst 1, and the loading of ruthenium dioxide in the catalyst with respect to the support was 2%.
The following evaluation tests were carried out on the performance of the above catalyst:
the catalysts 1 to 6 in the examples and the catalyst 1 in the comparative example were tabletted, crushed and granulated to obtain 40 to 60 mesh catalyst particles. Then 0.1g of 40-60 mesh catalyst is uniformly mixed with 0.6g of quartz sand with the same mesh number, and the mixture is filled into a fixed bed quartz reactor with the inner diameter of 6 mm.
The reaction conditions were as follows: the reaction raw material gas is HCl/O22, the reaction temperature is 320 ℃, the reaction pressure is 0.1MPa, and the gas-phase space velocity is 36000ml/h.g-cat。
After the reaction is stabilized for 2h, KI solution with the mass concentration of 20% is used for absorbing gas at the outlet of the reactor. Then using 0.14mol/L NaS2O3The solution titrates the absorption solution, and the generation amount of chlorine gas is calculated. The conversion of HCl and the space-time yield per molar amount of ruthenium were calculated according to the formulae described in the present specification and the results are shown in Table 1.
TABLE 1 hydrogen chloride oxidation reaction Performance of different catalysts
As can be seen from Table 1, the loading of ruthenium dioxide in the catalyst synthesized by the method of the invention is in the range of 0.5-5%, and the utilization efficiency of ruthenium is kept at a high level. Although the catalyst 4 has the same loading as the comparative catalyst 1, the space-time yield of ruthenium per molar amount of the catalyst 4 is significantly improved, which indicates that the method of the present invention can contribute to the increase in the utilization efficiency of the noble metal ruthenium.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A preparation method of a hydrogen chloride oxidation catalyst is characterized by comprising the following steps: firstly, respectively weighing a ruthenium precursor aqueous solution, a hydrogen peroxide solution and a powder carrier according to the molar ratio of (0.3-3) to (0.5-10) to 100 of the ruthenium precursor, then adding the powder carrier into the ruthenium precursor aqueous solution, dropwise adding the hydrogen peroxide solution after fully stirring, uniformly mixing, heating to 80-100 ℃, preserving the temperature for 1-10 h, then adjusting the pH value of the solution to 6-12 by using alkali, finally performing solid-liquid separation treatment, and drying the separated solid to obtain the hydrogen chloride oxidation catalyst.
2. The method for preparing a hydrogen chloride oxidation catalyst according to claim 1, wherein the ruthenium precursor is anhydrous ruthenium trichloride or hydrated ruthenium trichloride; the mass concentration of ruthenium in the ruthenium precursor aqueous solution is 0.1-5%.
3. The method for preparing a hydrogen chloride oxidation catalyst according to claim 1, wherein the mass concentration of the hydrogen peroxide solution is 10% to 50%.
4. The method of claim 1, wherein the powder carrier is a composite of titanium dioxide and at least one of lanthanum oxide, cerium oxide, aluminum oxide, silicon dioxide, nickel oxide and cobaltosic oxide, or titanium dioxide or/and tin dioxide.
5. The method for preparing a hydrogen chloride oxidation catalyst according to claim 1, wherein the alkali is any one or more of water glass, sodium metasilicate and sodium metaaluminate.
6. The method for preparing a hydrogen chloride oxidation catalyst according to claim 1, wherein the active component in the hydrogen chloride oxidation catalyst is ruthenium dioxide, and the mass ratio of the ruthenium dioxide to the support is (0.1-1): 20.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201013A (en) * | 1997-06-03 | 1998-12-09 | 住友化学工业株式会社 | Process for preparing chlorine gas |
| CN1522176A (en) * | 2002-04-26 | 2004-08-18 | ס�ѻ�ѧ��ҵ��ʽ���� | Method for preparing ruthenium-carrying alumina and method for oxidizing alcohol |
| CN1806914A (en) * | 2006-02-23 | 2006-07-26 | 华南理工大学 | Method for preparing carbon nanotube supported nanometer hydrated ruthenium oxide |
| EP2142297A1 (en) * | 2007-04-24 | 2010-01-13 | Basf Se | Porous organometallic framework materials loaded with catalyst metal components |
| CN102513102A (en) * | 2011-11-22 | 2012-06-27 | 北京化工大学 | Preparation method and application of titanium dioxide loaded ruthenium catalyst |
| CN103480371A (en) * | 2013-09-22 | 2014-01-01 | 中国神华能源股份有限公司 | Denitration and demercuration catalyst as well as preparing method and application thereof |
| CN103480271A (en) * | 2013-09-22 | 2014-01-01 | 中国神华能源股份有限公司 | Smoke treatment method |
| CN105879866A (en) * | 2016-05-03 | 2016-08-24 | 中国科学院大学 | Efficient Deacon reaction catalyst |
-
2017
- 2017-11-29 CN CN201711220899.8A patent/CN107952432B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201013A (en) * | 1997-06-03 | 1998-12-09 | 住友化学工业株式会社 | Process for preparing chlorine gas |
| CN1522176A (en) * | 2002-04-26 | 2004-08-18 | ס�ѻ�ѧ��ҵ��ʽ���� | Method for preparing ruthenium-carrying alumina and method for oxidizing alcohol |
| CN1806914A (en) * | 2006-02-23 | 2006-07-26 | 华南理工大学 | Method for preparing carbon nanotube supported nanometer hydrated ruthenium oxide |
| EP2142297A1 (en) * | 2007-04-24 | 2010-01-13 | Basf Se | Porous organometallic framework materials loaded with catalyst metal components |
| CN102513102A (en) * | 2011-11-22 | 2012-06-27 | 北京化工大学 | Preparation method and application of titanium dioxide loaded ruthenium catalyst |
| CN103480371A (en) * | 2013-09-22 | 2014-01-01 | 中国神华能源股份有限公司 | Denitration and demercuration catalyst as well as preparing method and application thereof |
| CN103480271A (en) * | 2013-09-22 | 2014-01-01 | 中国神华能源股份有限公司 | Smoke treatment method |
| CN105879866A (en) * | 2016-05-03 | 2016-08-24 | 中国科学院大学 | Efficient Deacon reaction catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Total oxidation of propane with a nano-RuO2/TiO2 catalyst;Damien P. Debecker，等;《Applied Catalysis A: General》;20140502;第11-18页 * |
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