WO2023016145A1 - Catalyseur d'hydrolyse de soufre organique approprié pour un procédé claus, son procédé de préparation, et son application - Google Patents

Catalyseur d'hydrolyse de soufre organique approprié pour un procédé claus, son procédé de préparation, et son application Download PDF

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WO2023016145A1
WO2023016145A1 PCT/CN2022/103875 CN2022103875W WO2023016145A1 WO 2023016145 A1 WO2023016145 A1 WO 2023016145A1 CN 2022103875 W CN2022103875 W CN 2022103875W WO 2023016145 A1 WO2023016145 A1 WO 2023016145A1
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metal
precursor
reaction
catalyst
concentration
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Chinese (zh)
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郝郑平
李铁军
魏征
张凤莲
蒋国霞
王震宇
张中申
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中国科学院大学
山东三维化学集团股份有限公司
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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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt

Definitions

  • the invention belongs to the technical field of sulfur recovery technology, and in particular relates to an organosulfur hydrolysis catalyst suitable for the Claus process and its preparation method and application.
  • the existing acid gas sulfur recovery process its main equipment includes a sulfur production burner along the gas flow direction, a two-stage Claus reactor, etc.
  • a high-temperature thermal reaction occurs in the combustion furnace for sulfur production, one-third of the H 2 S in the feed gas is burned into SO 2 , and two-thirds of the H 2 S reacts with the generated SO 2 to leave the combustion
  • the mixed gas in the chamber is cooled, and then the liquid sulfur is separated, and the gas enters the two-stage Claus reactor successively to undergo Claus catalytic reaction, which further improves the sulfur recovery rate and converts H 2 S in the acid gas into sulfur for recovery.
  • the acid gas contains impurities such as hydrocarbons, many side reactions will occur, such as:
  • H 2 S H 2 +0.5S 2 -89.2KJ/mol
  • Organic sulfur (mainly COS and CS 2 ) exists in a large amount in the sulfur process gas after being produced by homemade sulfur combustion furnaces. Affected by the concentrations of hydrocarbons and CO 2 in the acid gas, the concentrations of COS and CS 2 in the process gas vary greatly.
  • the on-site detection of the on-site operating device is basically in the range of 2000-10000ppm.
  • existing Claus catalysts and hydrogenation catalysts can convert part of COS and CS 2 into H 2 O and CO 2 through hydrolysis, the hydrolysis of organic sulfur by Claus catalysts and hydrogenation catalysts is affected by temperature great. Although the hydrolysis rate of organic sulfur can reach more than 90% above 315°C, the high temperature at this time inhibits the progress of the Claus reaction.
  • Organic sulfur hydrolysis catalysts mainly include alumina system and titanium oxide system.
  • the alumina system has high hydrolysis activity, but the material has poor sulfur resistance and is prone to sulfur accumulation and deactivation.
  • the titanium oxide system has a strong ability to resist sulfur accumulation, its hydrolysis performance is poor, which cannot meet the demand for organic sulfur removal under the conditions of the Claus reaction dominant zone.
  • Chinese patent CN1159209C discloses a medium-temperature sulfur-resistant organosulfur hydrolysis catalyst, which is characterized in that it has good performance in hydrolyzing 20-1500ppm organosulfur at 85-250°C. It is characterized in that before the decarburization of the raw material gas and fine desulfurization at normal temperature, a medium-temperature sulfur-resistant hydrolysis catalyst is introduced.
  • the catalyst contains H 2 S 50-10000ppm and COS 20-1500ppm in the raw gas, and the O 2 content is 5-6000ppm.
  • the pressure is normal pressure- 30MPa, the temperature is 85-250°C, it has a good effect on the hydrolysis of organic sulfur, but it does not involve the treatment of CS 2.
  • CS 2 often coexists with COS, and its concentration is usually an order of magnitude lower than that of COS, but it is more difficult to hydrolyze. Major issues with organosulfur hydrolysis in Rolls process gases.
  • Chinese patent CN108246303B discloses a catalyst for hydrolysis of Claus tail gas, characterized in that the catalyst is supported by activated alumina, and the activated alumina is loaded with cobalt oxide, cesium oxide and molybdenum oxide.
  • the catalyst has excellent performance and can achieve a removal rate of 95.6% of CS 2 at 240°C.
  • this method requires hydrogen and has high cost, and the concentration of CS 2 to be treated is low, only 500ppm. blank.
  • Chinese patent CN109126830A provides a titanium dioxide-based sulfur recovery catalyst, which is characterized in that it contains 70-88% of titanium oxide, 10-20% of silicon carbide, 1-5% of calcium oxide and sodium oxide, 1-5% catalyst additives.
  • the catalyst has excellent hydrolysis performance for high-concentration CS 2 , but the reaction temperature is 280°C, which is not conducive to the Claus reaction.
  • Perovskite composite oxides refer to a class of metal oxides with the general molecular formula ABO x .
  • the A site is generally a rare earth, alkali or alkaline earth metal ion, and the B site is a transition metal ion.
  • This material has abundant surface acid
  • the advantages of base sites and oxygen vacancies, excellent acid-base catalytic performance and thermal stability have been widely used in catalysis.
  • a large number of studies have shown that the hydrolysis reaction of organosulfur is a typical base-catalyzed reaction, and the basic site is generally considered to be the active center of the hydrolysis reaction. Therefore, the present invention uses a simple hydrothermal method to synthesize a perovskite-type composite oxide catalyst. Alkali metals or alkaline earth metals are selected for the A site, and transition metals are selected for the B site. The materials exhibit excellent hydrolysis reactivity.
  • the object of the present invention is to provide a medium-temperature organosulfur hydrolysis catalyst suitable for the Claus process, which can remove the organosulfur in the process gas under the condition of the Claus reaction dominant zone, Thereby improving the total sulfur yield of the sulfur plant and achieving the goal of ultra-low emission from the sulfur plant; the invention also provides its preparation method and application.
  • alkali metal compounds including NaOH, KOH, Na 2 CO 3 , K 2 CO 3
  • ABO x perovskite type composite oxide catalyst
  • the preparation method of the organosulfur hydrolysis catalyst applicable to the Claus process of the present invention comprises the following steps:
  • step (2) under vigorous stirring conditions, the precursor of metal B is added to the aqueous solution obtained in step (1);
  • step (3) adding the alkali metal compound to the aqueous solution obtained in step (2);
  • step (3) (4) Stir the aqueous solution obtained in step (3) for 0.5-3 hours, then move it into a hydrothermal reaction kettle, and keep it at 100-200°C for 12-48 hours;
  • step (4) After centrifuging and washing the aqueous solution obtained in step (4), drying at a temperature of 100-150° C. for 6-18 hours to obtain a powder;
  • the precursor of metal A is metal A nitrate, carbonate or acetate.
  • the precursor of metal B is divided into the precursor of metal Ti and the precursor of metal Fe, Co, the precursor of metal Ti is tetraisopropyl titanate or tetrabutyl titanate, the precursor of metal Fe, Co Nitrate, carbonate or acetate of Fe and Co.
  • the alkali metal compound is one or more of NaOH, KOH, Na 2 CO 3 or K 2 CO 3 .
  • the application of the organosulfur hydrolysis catalyst applicable to Claus process of the present invention is used in the catalytic hydrolysis process of Claus process organosulfur, wherein: COS concentration is 10 ⁇ 10000ppm, CS 2 concentration is 10 ⁇ 10000ppm, The H 2 S concentration is 0-20000ppm, the SO 2 concentration is 0-10000ppm, the reaction temperature is 180-320°C, and the space velocity is 1000-10000h -1 .
  • the perovskite-type composite oxide catalyst component and structure of the present invention are highly adjustable, and the surface has abundant acid-base sites and oxygen vacancies.
  • perovskite-type composite oxide catalysts in the Claus organic sulfur catalytic hydrolysis process can realize efficient hydrolysis of organic sulfur, thereby achieving ultra-low emissions from sulfur recovery units.
  • Fig. 1 is the COS catalytic hydrolysis activity figure on the perovskite type composite oxide catalyst (embodiment 2-4) of different compositions, evaluation example 1;
  • Fig. 2 is the CS on the perovskite type composite oxide catalyst (embodiment 1-7) of different compositions Catalytic hydrolysis activity figure, evaluation example 2;
  • Fig. 3 is COS catalytic hydrolysis activity diagram (a) and CS 2 catalytic hydrolysis activity diagram (b) on perovskite type composite oxide catalyst embodiment 3 under different reaction background atmospheres, evaluation examples 1, 2, 3, 4, 5, 6;
  • FIG. 4 is a graph showing the catalytic hydrolysis stability of COS and CS 2 at 250° C. on the perovskite-type composite oxide catalyst Example 3, Evaluation Examples 7 and 8.
  • FIG. 4 is a graph showing the catalytic hydrolysis stability of COS and CS 2 at 250° C. on the perovskite-type composite oxide catalyst Example 3, Evaluation Examples 7 and 8.
  • FIG. 4 is a graph showing the catalytic hydrolysis stability of COS and CS 2 at 250° C. on the perovskite-type composite oxide catalyst Example 3, Evaluation Examples 7 and 8.
  • the catalytic material samples of Examples 2, 3, and 4 were ground, pressed into tablets, and sieved, and the 40-60 mesh parts were taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • reaction gas composition (volume) is COS 5000ppm, H 2 O 6000ppm, H 2 S 5000ppm, SO 2 2500ppm, the rest is N 2 , gas volume space velocity is 3000h -1 , bed temperature is 200, 250 and 300°C, keep at each temperature point for 5 hours, take the average value of the data in the last 1 hour as the activity data at that temperature point.
  • Catalyst activity in this reaction is expressed by the conversion of COS, where:
  • COS conversion rate (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
  • the catalytic material samples of Examples 1, 2, 3, 4, 5, 6, and 7 were ground, pressed into tablets, and sieved, and the 40-60 mesh parts were taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • Catalyst evaluation conditions the reaction gas composition (volume) is CS 2 2000ppm, H 2 O 4800ppm, H 2 S 5000ppm, SO 2 2500ppm, the remainder is N 2 , the gas volume space velocity is 3000h -1 , and the bed temperature is 200, 250 and 300°C, each temperature point was kept for 5 hours, and the average value of the data in the last 1 hour was taken as the activity data at that temperature point.
  • Catalyst activity in this reaction is expressed by the conversion of CS2 , where:
  • CS 2 conversion rate (CS 2 concentration in the intake air-residual CS 2 concentration in the outlet air)/CS 2 concentration in the intake air*100%.
  • the catalytic material sample of Example 3 was ground, pressed into tablets, and sieved, and the 40-60 mesh part was taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • reaction gas composition (volume) is COS 5000ppm, H 2 O 6000ppm, H 2 S0ppm, SO 2 0ppm, balance is N 2 , gas volume space velocity is 3000h -1 , bed temperature is 200, 250 and 300 °C, each temperature point is maintained for 5 hours, and the average value of the data in the last 1 hour is taken as the activity data of the temperature point.
  • Catalyst activity in this reaction is expressed by the conversion of COS, where:
  • COS conversion rate (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
  • the catalytic material sample of Example 3 was ground, pressed into tablets, and sieved, and the 40-60 mesh part was taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • reaction gas composition (volume) is CS 2 2000ppm, H 2 O 4800ppm, H 2 S0ppm, SO 2 0ppm, the balance is N 2 , the gas volume space velocity is 3000h -1 , the bed temperature is 200, 250 and 300°C, keep at each temperature point for 5h, take the average value of the data in the last 1h as the activity data at that temperature point.
  • Catalyst activity in this reaction is expressed by the conversion of CS2 , where:
  • CS 2 conversion rate (CS 2 concentration in the intake air-residual CS 2 concentration in the outlet air)/CS 2 concentration in the intake air*100%.
  • the catalytic material sample of Example 3 was ground, pressed into tablets, and sieved, and the 40-60 mesh part was taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • Catalyst evaluation conditions the reaction gas composition (volume) is COS 10000ppm, H 2 O 12000ppm, H 2 S 20000ppm, SO 2 10000ppm, the balance is N 2 , the gas volume space velocity is 3000h -1 , the bed temperature is 200, 250 and 300°C, keep at each temperature point for 3 hours, take the average value of the data in the last 1 hour as the activity data at that temperature point.
  • Catalyst activity in this reaction is expressed by the conversion of COS, where:
  • COS conversion rate (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
  • the catalytic material sample of Example 3 was ground, pressed into tablets, and sieved, and the 40-60 mesh part was taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • Catalyst evaluation conditions the reaction gas composition (volume) is CS 2 10000ppm, H 2 O 24000ppm, H 2 S 20000ppm, SO 2 10000ppm, the remainder is N 2 , the gas volume space velocity is 3000h -1 , and the bed temperature is 200, 250 And 300°C, each temperature point is kept for 3 hours, and the average value of the data in the last 1 hour is taken as the activity data of this temperature point.
  • Catalyst activity in this reaction is expressed by the conversion of CS2 , where:
  • CS 2 conversion rate (CS 2 concentration in the intake air-residual CS 2 concentration in the outlet air)/CS 2 concentration in the intake air*100%.
  • the catalytic material sample of Example 3 was ground, pressed into tablets, and sieved, and the 40-60 mesh part was taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • reaction gas composition (volume) is COS 5000ppm, H 2 O 6000ppm, H 2 S 5000ppm, SO 2 2500ppm, the rest is N 2 , the gas volume space velocity is 3000h -1 , the bed temperature is constant at 250°C and kept for 40h , take the average value of the 40h data as the activity data.
  • Catalyst activity in this reaction is expressed by the conversion of COS, where:
  • COS conversion rate (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
  • the catalytic material sample of Example 3 was ground, pressed into tablets, and sieved, and the 40-60 mesh part was taken, and the activity evaluation of the catalyst was carried out in the organosulfur hydrolysis evaluation device.
  • the quartz fixed bed reaction tube has an outer diameter of 10 mm and an inner diameter of 6 mm.
  • the reaction furnace adopts electric heating, two-stage heating, the total length of the heating section is 350mm, and the loading amount of catalyst is 0.5ml.
  • the raw material gas is mixed and then enters the reactor for reaction. After the reaction, the gas composition and concentration are analyzed by gas chromatography with a thermal conductivity detector (TCD) and a flame photometric detector (FPD+).
  • TCD thermal conductivity detector
  • FPD+ flame photometric detector
  • Catalyst evaluation conditions the reaction gas composition (volume) is CS 2 2000ppm, H 2 O 4800ppm, H 2 S 5000ppm, SO 2 2500ppm, the rest is N 2 , the gas volume space velocity is 3000h -1 , the bed temperature is constant at 250°C, kept 40h, take the average value of the 40h data as the activity data.
  • Catalyst activity in this reaction is expressed by the conversion of CS2 , where:
  • CS 2 conversion rate (CS 2 concentration in the intake air-residual CS 2 concentration in the outlet air)/CS 2 concentration in the intake air*100%.
  • the perovskite-type composite oxide catalyst prepared by the method of the present invention has excellent hydrolysis activity and has the ability to efficiently treat organic sulfur in the Claus process.

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Abstract

L'invention concerne un catalyseur d'hydrolyse de soufre organique approprié pour le procédé Claus et son procédé de préparation. Le catalyseur a la formule générale de ABOx et est synthétisé au moyen d'un procédé hydrothermique, A étant un élément de métal alcalin ou alcalino-terreux, comprenant Na, K, Cs, Mg, Ca, Sr et Ba, B étant un élément de métal de transition, comprenant Ti, Fe et Co, et x = 1,5-3. Ce type de matériau présente les caractéristiques d'une forte composition et d'une capacité d'ajustement de structure et de sites acides et alcalins de surface riche, et présente une excellente activité d'hydrolyse catalytique de soufre organique.
PCT/CN2022/103875 2021-08-09 2022-07-05 Catalyseur d'hydrolyse de soufre organique approprié pour un procédé claus, son procédé de préparation, et son application WO2023016145A1 (fr)

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CN113663665B (zh) * 2021-08-09 2023-09-22 中国科学院大学 适用于克劳斯工艺的有机硫水解催化剂及其制备方法和应用
CN114649527B (zh) * 2022-02-24 2023-05-09 南京工业大学 一种四相导体质子导体氧电极材料、制备方法及用途

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