WO2023016145A1 - Organic sulfur hydrolysis catalyst suitable for claus process, preparation method therefor, and application thereof - Google Patents

Organic sulfur hydrolysis catalyst suitable for claus process, preparation method therefor, and application thereof 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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Publication of WO2023016145A1 publication Critical patent/WO2023016145A1/en

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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.

Abstract

An organic sulfur hydrolysis catalyst suitable for the Claus process and a preparation method therefor. The catalyst has the general formula of ABOx and is synthesized using a hydrothermal method, wherein A is an alkali or alkaline earth metal element, including Na, K, Cs, Mg, Ca, Sr, and Ba, B is a transition metal element, including Ti, Fe, and Co, and x=1.5-3. This type of material has the characteristics of strong composition and structure adjustability and rich surface acidic and alkaline sites, and has excellent organic sulfur catalytic hydrolysis activity.

Description

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Organosulfur hydrolysis catalyst suitable for Claus process, preparation method and application thereof 技术领域technical field
本发明属于硫磺回收工艺技术领域，具体涉及一种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。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.
背景技术Background technique
现有酸性气硫磺回收工艺，其主要设备包括沿气流方向的制硫燃烧炉、两级克劳斯反应器等。在制硫燃烧炉中发生高温热反应，进料气中三分之一的H 2S被燃烧成SO 2，三分之二的H 2S与生成的SO 2发生克劳斯反应，离开燃烧室的混合气体被冷却，然后液体硫磺被分离，气体再先后进入两级克劳斯反应器发生克劳斯催化反应，进一步提高硫磺回收率将酸性气体中的H 2S转化为硫磺回收。 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.
克劳斯制硫反应总反应方程式可表示如下：The overall reaction equation of the Claus sulfur reaction can be expressed as follows:
H 2S+0.5SO 2＝0.75S 2+H 2O-47.06KJ/mol。 H 2 S+0.5SO 2 =0.75S 2 +H 2 O-47.06KJ/mol.
由于酸性气中含有烃类等杂质，将出现诸多副反应，例如：Because the acid gas contains impurities such as hydrocarbons, many side reactions will occur, such as:
H 2S＝H 2+0.5S 2-89.2KJ/mol， H 2 S=H 2 +0.5S 2 -89.2KJ/mol,
CO 2+0.5H 2S＝CO+0.5H 2+0.5SO 2-281.5KJ/mol， CO 2 +0.5H 2 S=CO+0.5H 2 +0.5SO 2 -281.5KJ/mol,
CO 2+1.5S＝COS+0.5SO 2+625.5KJ/mol， CO 2 +1.5S=COS+0.5SO 2 +625.5KJ/mol,
CO 2+3S 1＝CS 2+2SO 2+967.9KJ/mol。 CO 2 +3S 1 =CS 2 +2SO 2 +967.9KJ/mol.
有机硫(主要是COS和CS 2)自制硫燃烧炉产生后大量存在于硫磺过程气中，受酸性气中烃类和CO 2浓度的影响，过程气中COS和CS 2浓度变化极大，经现场运行装置实地检测基本处于检测2000～10000ppm的范围。虽然现有的克劳斯催化剂和加氢催化剂可以通过水解反应将部分COS和CS 2转化为H 2O和CO 2，但克劳斯催化剂和加氢催化剂对于有机硫的水解作用受温度的影响极大。在315℃以上有机硫的水解率虽可达90％以上，但此时高温抑制了克劳斯反应的进行，而在220～250℃的克劳斯反应优势区，有机硫的水解率由于温度的降低迅速下降，无法满足有机硫脱除要求，导致硫磺回收装置总硫排放居高不下。现有硫磺回收领域催化剂专利技术多针对于克劳斯反应及加氢反应，这些催化剂虽具有一定的有机硫水解反应活性，但其实际应用仍存在诸多局限。目前，有关针对于硫磺回收领域的单独有机硫水解专利技术尚未见诸报导。 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. Although 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. The rapid decline in the reduction of organic sulfur cannot meet the requirements of organic sulfur removal, resulting in high total sulfur emissions from sulfur recovery units. Most of the existing catalyst patent technologies in the field of sulfur recovery are aimed at the Claus reaction and hydrogenation reaction. Although these catalysts have certain activity in the hydrolysis of organic sulfur, there are still many limitations in their practical application. At present, there is no report on a single patented technology for organic sulfur hydrolysis in the field of sulfur recovery.
有机硫水解催化剂主要有氧化铝体系以及氧化钛体系。氧化铝体系水解活性较高，但材料耐硫性能较差，易积硫失活。氧化钛体系虽具有较强的抗积硫能力，但其水解性能较差，无法满足克劳斯反应优势区工况下的有机硫脱除需求。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. Although 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.
中国专利CN1159209C公开了一种中温耐硫有机硫水解催化剂，其特征在于在85-250℃对20-1500ppm的有机硫水解性能良好。其特征是在原料气脱碳、常温精脱硫前，引入中温耐硫水解催化剂，该催化剂在原料气中H 2S 50-10000ppm和COS 20-1500ppm，O 2含量5-6000ppm，压力常压-30MPa，温度85-250℃条件下对于有机硫水解效果良好，但其并未涉及对于CS 2的处理，CS 2常常与COS共存，其浓度通常低于COS一个数量级但其更难水解，是克劳斯过程气中有机硫水解的主要问题。 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℃, 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.
中国专利CN108246303B公开了一种用于克劳斯尾气加氢水解的催化剂，其特征在于，所述催化剂以活性氧化铝为载体，所述活性氧化铝上负载有氧化钴、氧化铯以及氧化钼。该催化剂性能卓越，240℃下可达到95.6％的CS 2去除率，但该方法需要氢气，成本较高，且所处理的CS 2浓度较低，仅为500ppm，在高浓度CS 2处理方面存在空白。 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. However, this method requires hydrogen and has high cost, and the concentration of CS 2 to be treated is low, only 500ppm. blank.
中国专利CN109126830A提供了一种二氧化钛基硫磺回收催化剂，其特征在于以催化剂重量百分比计，包含70-88％的氧化钛、10-20％的碳化硅、1-5％的氧化钙和氧化钠、1-5％的催化剂助剂。该催化剂对于高浓度CS 2水解性能优异，但反应温度为280℃，温度较高不利于克劳斯反应的进行。 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.
钙钛矿型复合氧化物是指一类分子通式为ABO x的金属氧化物，其A位为一般为稀土、碱或碱土金属离子，B位为过渡金属离子，该材料具有丰富的表面酸碱位和氧空位，优异的酸碱催化性能和热稳定性等优点，在催化方面得到了广泛的应用。大量研究表明，有机硫水解反应是典型的碱催化反应，碱性位点通常被认为是水解反应的活性中心。因此，本发明采用简便的水热法合成了钙钛矿型复合氧化物催化剂，A位选取碱金属或碱土金属，B位选取过渡金属，材料表现出了优异的水解反应活性。 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.
发明内容Contents of the invention
针对现有技术的不足，本发明的目的是提供一种适用于克劳斯工艺的中温有机硫水解催化剂，该催化剂可在克劳斯反应优势区工况下，去除过程气中的有机硫，从而提高硫磺装置总硫收率，以及达到硫磺装置超低排放的目的；本发明同时提供其制备方法和应用。Aiming at the deficiencies in the prior art, 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.
本发明是采用以下技术方案实现的：The present invention is realized by adopting the following technical solutions:
本发明所述的适用于克劳斯工艺的有机硫水解催化剂，该催化剂的通式为：ABO x，其中A＝Na、K、Cs、Mg、Ca、Sr或Ba中的一种，B＝Ti、Fe或Co中的一种。 The organosulfur hydrolysis catalyst suitable for the Claus process described in the present invention has a general formula: ABO x , wherein A=one of Na, K, Cs, Mg, Ca, Sr or Ba, B= One of Ti, Fe or Co.
本发明采用水热法，以碱金属化合物(包括NaOH、KOH、Na 2CO 3、K 2CO 3)为沉淀剂，合成钙钛矿型复合氧化物催化剂(ABO x，其中A＝Na、K、Cs、Mg、Ca、Sr、Ba，B＝Ti、Fe、Co，x＝1.5-3)。 The present invention adopts a hydrothermal method and uses alkali metal compounds (including NaOH, KOH, Na 2 CO 3 , K 2 CO 3 ) as a precipitating agent to synthesize a perovskite type composite oxide catalyst (ABO x , wherein A=Na, K , Cs, Mg, Ca, Sr, Ba, B=Ti, Fe, Co, x=1.5-3).
具体地，本发明所述的适用于克劳斯工艺的有机硫水解催化剂的制备方法，包括以下步骤：Specifically, the preparation method of the organosulfur hydrolysis catalyst applicable to the Claus process of the present invention comprises the following steps:
(1)将金属A的前驱体溶于水中，形成含金属A的水溶液；(1) dissolving the precursor of metal A in water to form an aqueous solution containing metal A;
(2)在剧烈搅拌条件下，将金属B的前驱体加入到步骤(1)所得的水溶液中；(2) under vigorous stirring conditions, the precursor of metal B is added to the aqueous solution obtained in step (1);
(3)将碱金属化合物加入到步骤(2)所得的水溶液中；(3) adding the alkali metal compound to the aqueous solution obtained in step (2);
(4)将步骤(3)所得水溶液搅拌0.5-3小时后移入水热反应釜中，100-200℃下保持12-48小时；(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;
(5)将步骤(4)所得水溶液离心、洗涤后，在100-150℃温度下干燥6-18小时，制得粉末；(5) 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;
(6)将粉末在450-850℃温度下焙烧4-8小时。(6) Calcining the powder at a temperature of 450-850° C. for 4-8 hours.
其中：in:
所述的金属A的前驱体为金属A的硝酸盐、碳酸盐或乙酸盐。The precursor of metal A is metal A nitrate, carbonate or acetate.
所述的金属B的前驱体分为金属Ti的前驱体和金属Fe、Co的前驱体，金属Ti的前驱体为钛酸四异丙酯或钛酸四丁酯，金属Fe、Co的前驱体为Fe、Co的硝酸盐、碳酸盐或乙酸盐。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.
所述的碱金属化合物是NaOH、KOH、Na 2CO 3或K 2CO 3中的一种或几种。 The alkali metal compound is one or more of NaOH, KOH, Na 2 CO 3 or K 2 CO 3 .
本发明所述的适用于克劳斯工艺的有机硫水解催化剂的应用，用于克劳斯工艺有机硫的催化水解过程中，其中：COS浓度为10～10000ppm，CS 2浓度为10～10000ppm，H 2S浓度为0～20000ppm，SO 2浓度为0～10000ppm，反应温度为180～320℃，空速为1000～10000h -1。 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 .
与现有技术相比，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
1)本发明所述的钙钛矿型复合氧化物催化剂组份和结构可调变性强，表面具有丰富的酸碱性位和氧空位。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.
2)钙钛矿型复合氧化物催化剂在克劳斯有机硫催化水解过程中的应用，可实现有机硫的高效水解，从而达到硫磺回收装置的超低排放。2) The application of 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.
3)本发明催化剂的制备方法，科学合理、简单易行。3) The preparation method of the catalyst of the present invention is scientific, reasonable, simple and feasible.
附图说明Description of drawings
图1为不同组成的钙钛矿型复合氧化物催化剂(实施例2-4)上的COS催化水解活性图，评价例1；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;
图2为不同组成的钙钛矿型复合氧化物催化剂(实施例1-7)上的CS 2催化水解活性图，评价例2； 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;
图3为不同反应背景气氛下钙钛矿型复合氧化物催化剂实施例3上的COS催化水解活性图(a)以及CS 2催化水解活性图(b)，评价例1、2、3、4、5、6； 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;
图4为钙钛矿型复合氧化物催化剂实施例3上250℃下的COS和CS 2的催化水解稳定性图，评价例7、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.
具体实施方式Detailed ways
下面列举具体实施例和附图对本发明进行进一步说明。需要说明的是本发明所列的这些具体实施例仅限于说明本发明，而非对本发明上述内容作任何意义上的限定。The present invention will be further described by enumerating specific embodiments and accompanying drawings below. It should be noted that these specific embodiments listed in the present invention are only for illustrating the present invention, rather than limiting the above content of the present invention in any sense.
实施例1Example 1
将7.692g六水硝酸镁溶于100mL去离子水中，在剧烈搅拌条件下，依次加入8.88mL钛酸四异丙酯、2.4g碱金属化合物氢氧化钠，搅拌1h。将所得溶液转移至容量为180mL的水热反应釜中，烘箱中200℃反应24h。取出溶液样品，用去离子水及乙醇离心、洗涤三次后，置于烘箱内120℃干燥12h。取出粉末样品，置于马弗炉内650℃焙烧6h，升温速率5℃/min，所得样品记为MT。Dissolve 7.692g of magnesium nitrate hexahydrate in 100mL of deionized water, add 8.88mL of tetraisopropyl titanate and 2.4g of alkali metal compound sodium hydroxide in sequence under vigorous stirring, and stir for 1 hour. The obtained solution was transferred to a hydrothermal reaction kettle with a capacity of 180 mL, and reacted in an oven at 200° C. for 24 h. The solution samples were taken out, centrifuged and washed three times with deionized water and ethanol, and dried in an oven at 120°C for 12 hours. The powder sample was taken out, placed in a muffle furnace and roasted at 650°C for 6h, with a heating rate of 5°C/min, and the obtained sample was denoted as MT.
实施例2Example 2
将7.085g四水硝酸钙溶于100mL去离子水中，在剧烈搅拌条件下，依次加入8.88mL钛酸四异丙酯、2.4g碱金属化合物氢氧化钠，搅拌1h。将所得溶液转移至容量为180mL的水热反应釜中，烘箱中200℃反应24h。取出溶液样品，用去离子水及乙醇离心、洗涤三次后，置于烘箱内120℃干燥12h。取出粉末样品，置于马弗炉内650℃焙烧6h，升温速率5℃/min，所得样品记为CT。Dissolve 7.085g of calcium nitrate tetrahydrate in 100mL of deionized water, add 8.88mL of tetraisopropyl titanate and 2.4g of alkali metal compound sodium hydroxide in sequence under vigorous stirring, and stir for 1 hour. The obtained solution was transferred to a hydrothermal reaction kettle with a capacity of 180 mL, and reacted in an oven at 200° C. for 24 h. The solution samples were taken out, centrifuged and washed three times with deionized water and ethanol, and dried in an oven at 120°C for 12 hours. The powder sample was taken out, placed in a muffle furnace and roasted at 650°C for 6h with a heating rate of 5°C/min, and the obtained sample was denoted as CT.
实施例3Example 3
将6.349g硝酸锶溶于100mL去离子水中，在剧烈搅拌条件下，依次加入8.88mL钛酸四异丙酯、2.4g碱金属化合物氢氧化钠，搅拌1h。将所得溶液转移至容量为180mL的水热反应釜中，烘箱中200℃反应24h。取出溶液样品，用去离子水及乙醇离心、洗涤三次后，置于烘箱内120℃干燥12h。取出粉末样品，置于马弗炉内650℃焙烧6h，升温速率5℃/min，所得样品记为ST。Dissolve 6.349g of strontium nitrate in 100mL of deionized water, add 8.88mL of tetraisopropyl titanate and 2.4g of alkali metal compound sodium hydroxide in sequence under vigorous stirring, and stir for 1 hour. The obtained solution was transferred to a hydrothermal reaction kettle with a capacity of 180 mL, and reacted in an oven at 200° C. for 24 h. The solution samples were taken out, centrifuged and washed three times with deionized water and ethanol, and dried in an oven at 120°C for 12 hours. The powder sample was taken out, placed in a muffle furnace and roasted at 650 °C for 6 h, the heating rate was 5 °C/min, and the obtained sample was marked as ST.
实施例4Example 4
将7.841g硝酸钡溶于100mL去离子水中，在剧烈搅拌条件下，依次加入8.88mL钛酸四异丙酯、2.4g碱金属化合物氢氧化钠，搅拌1h。将所得溶液转移至容量为180mL的水热反应釜中，烘箱中200℃反应24h。取出溶液样品，用去离子水及乙醇离心、洗涤三次后，置于烘箱内120℃干燥12h。取出粉末样品，置于马弗炉内650℃焙烧6h，升温速率5℃/min，所得样品记为BT。Dissolve 7.841g of barium nitrate in 100mL of deionized water, add 8.88mL of tetraisopropyl titanate and 2.4g of alkali metal compound sodium hydroxide in sequence under vigorous stirring, and stir for 1 hour. The obtained solution was transferred to a hydrothermal reaction kettle with a capacity of 180 mL, and reacted in an oven at 200° C. for 24 h. The solution samples were taken out, centrifuged and washed three times with deionized water and ethanol, and dried in an oven at 120°C for 12 hours. The powder sample was taken out, placed in a muffle furnace and roasted at 650°C for 6h with a heating rate of 5°C/min, and the obtained sample was denoted as BT.
实施例5Example 5
将6.349g硝酸锶溶于100mL去离子水中，在剧烈搅拌条件下，依次加入3.511g乙酸钴、 2.4g碱金属化合物氢氧化钠，搅拌1h。将所得溶液转移至容量为180mL的水热反应釜中，烘箱中200℃反应24h。取出溶液样品，用去离子水及乙醇离心、洗涤三次后，置于烘箱内120℃干燥12h。取出粉末样品，置于马弗炉内650℃焙烧6h，升温速率5℃/min，所得样品记为SCT。Dissolve 6.349g of strontium nitrate in 100mL of deionized water, add 3.511g of cobalt acetate and 2.4g of alkali metal compound sodium hydroxide in sequence under vigorous stirring, and stir for 1 hour. The obtained solution was transferred to a hydrothermal reaction kettle with a capacity of 180 mL, and reacted in an oven at 200° C. for 24 h. The solution samples were taken out, centrifuged and washed three times with deionized water and ethanol, and dried in an oven at 120°C for 12 hours. The powder sample was taken out, placed in a muffle furnace and roasted at 650°C for 6h with a heating rate of 5°C/min, and the obtained sample was denoted as SCT.
实施例6Example 6
将6.169g乙酸锶溶于100mL去离子水中，在剧烈搅拌条件下，依次加入10.25ml钛酸四丁酯、1.2g氢氧化钠以及3.18g碳酸钠碱金属化合物，搅拌0.5h。将所得溶液转移至容量为180mL的水热反应釜中，烘箱中150℃反应12h。取出溶液样品，用去离子水及乙醇离心、洗涤三次后，置于烘箱内100℃干燥6h。取出粉末样品，置于马弗炉内450℃焙烧4h，升温速率5℃/min，所得样品记为ST-2。Dissolve 6.169g of strontium acetate in 100mL of deionized water, add 10.25ml of tetrabutyl titanate, 1.2g of sodium hydroxide and 3.18g of sodium carbonate alkali metal compound in sequence under vigorous stirring, and stir for 0.5h. The obtained solution was transferred to a hydrothermal reaction kettle with a capacity of 180 mL, and reacted in an oven at 150° C. for 12 h. The solution samples were taken out, centrifuged and washed three times with deionized water and ethanol, and dried in an oven at 100°C for 6 hours. Take out the powder sample, place it in a muffle furnace and bake it at 450°C for 4h with a heating rate of 5°C/min, and the obtained sample is designated as ST-2.
实施例7Example 7
将4.146g碳酸钾溶于100mL去离子水中，在剧烈搅拌条件下，依次加入12.12g九水硝酸铁、1.683g氢氧化钾以及4.146g碳酸钾碱金属化合物，搅拌3h。将所得溶液转移至容量为180mL的水热反应釜中，烘箱中200℃反应48h。取出溶液样品，用去离子水及乙醇离心、洗涤三次后，置于烘箱内150℃干燥18h。取出粉末样品，置于马弗炉内850℃焙烧8h，升温速率5℃/min，所得样品记为KF。Dissolve 4.146g of potassium carbonate in 100mL of deionized water, add 12.12g of ferric nitrate nonahydrate, 1.683g of potassium hydroxide and 4.146g of potassium carbonate alkali metal compound in sequence under vigorous stirring, and stir for 3 hours. The obtained solution was transferred to a hydrothermal reaction kettle with a capacity of 180 mL, and reacted in an oven at 200° C. for 48 h. The solution samples were taken out, centrifuged and washed three times with deionized water and ethanol, and dried in an oven at 150°C for 18 hours. The powder sample was taken out, placed in a muffle furnace and roasted at 850°C for 8h with a heating rate of 5°C/min, and the obtained sample was denoted as KF.
评价例1Evaluation Example 1
将实施例2、3、4催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为COS 5000ppm，H 2O 6000ppm，H 2S 5000ppm，SO 2 2500ppm，余为N 2，气体体积空速3000h -1，床层温度依次为200、250以及300℃，每个温度点保持5h，取最后1h的数据平均值为该温度点的活性数据。在该反应中催化剂活性通过COS的转化率来表示，其中： 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+). Catalyst evaluation conditions: 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转化率＝(进气中COS浓度-出气中剩余COS浓度)/进气中COS浓度*100％。COS conversion rate = (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
评价例2Evaluation example 2
将实施例1、2、3、4、5、6、7催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度 检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为CS 2 2000ppm，H 2O 4800ppm，H 2S 5000ppm，SO 2 2500ppm，余为N 2，气体体积空速3000h -1，床层温度依次为200、250以及300℃，每个温度点保持5h，取最后1h的数据平均值为该温度点的活性数据。在该反应中催化剂活性通过CS 2的转化率来表示，其中： 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+). 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转化率＝(进气中CS 2浓度-出气中剩余CS 2浓度)/进气中CS 2浓度*100％。 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%.
评价例3Evaluation example 3
将实施例3催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为COS 5000ppm，H 2O 6000ppm，H 2S0ppm，SO 2 0ppm，余为N 2，气体体积空速3000h -1，床层温度依次为200、250以及300℃，每个温度点保持5h，取最后1h的数据平均值为该温度点的活性数据。在该反应中催化剂活性通过COS的转化率来表示，其中： 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+). Catalyst evaluation conditions: 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 ℃, 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转化率＝(进气中COS浓度-出气中剩余COS浓度)/进气中COS浓度*100％。COS conversion rate = (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
评价例4Evaluation example 4
将实施例3催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为CS 2 2000ppm，H 2O 4800ppm，H 2S0ppm，SO 2 0ppm，余为N 2，气体体积空速3000h -1，床层温度依次为200、250以及300℃，每个温度点保持5h，取最后1h的数据平均值为该温度点的活性数据。在该反应中催化剂活性通过CS 2的转化率来表示，其中： 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+). Catalyst evaluation conditions: 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转化率＝(进气中CS 2浓度-出气中剩余CS 2浓度)/进气中CS 2浓度*100％。 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%.
评价例5Evaluation Example 5
将实施例3催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为COS 10000ppm，H 2O 12000ppm， H 2S 20000ppm，SO 2 10000ppm，余为N 2，气体体积空速3000h -1，床层温度依次为200、250以及300℃，每个温度点保持3h，取最后1h的数据平均值为该温度点的活性数据。在该反应中催化剂活性通过COS的转化率来表示，其中： 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+). 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转化率＝(进气中COS浓度-出气中剩余COS浓度)/进气中COS浓度*100％。COS conversion rate = (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
评价例6Evaluation example 6
将实施例3催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为CS 2 10000ppm，H 2O 24000ppm，H 2S 20000ppm，SO 2 10000ppm，余为N 2，气体体积空速3000h -1，床层温度依次为200、250以及300℃，每个温度点保持3h，取最后1h的数据平均值为该温度点的活性数据。在该反应中催化剂活性通过CS 2的转化率来表示，其中： 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+). 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转化率＝(进气中CS 2浓度-出气中剩余CS 2浓度)/进气中CS 2浓度*100％。 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%.
评价例7Evaluation example 7
将实施例3催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为COS 5000ppm，H 2O 6000ppm，H 2S5000ppm，SO 2 2500ppm，余为N 2，气体体积空速3000h -1，床层温度恒定为250℃，保持40h，取40h的数据平均值为活性数据。在该反应中催化剂活性通过COS的转化率来表示，其中： 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+). Catalyst evaluation conditions: 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转化率＝(进气中COS浓度-出气中剩余COS浓度)/进气中COS浓度*100％。COS conversion rate = (COS concentration in the intake air - residual COS concentration in the outlet air) / COS concentration in the intake air * 100%.
评价例8Evaluation example 8
将实施例3催化材料样品研磨、压片、过筛，取40-60目部分，在有机硫水解评价装置进行催化剂的活性评价。石英固定床反应管外径10mm，内径6mm。反应炉采用电加热，两段式加热，加热段总长度350mm，催化剂装填量各0.5ml。原料气经混合后进反应器进行反应，反应后气体成分及浓度使用带有热导检测器(TCD)以及火焰光度检测器(FPD+)的气相色谱进行分析。催化剂评价条件：反应气组成(体积)为CS 2 2000ppm，H 2O 4800ppm，H 2S5000ppm，SO 2 2500ppm，余为N 2，气体体积空速3000h -1，床层温度恒定为250℃，保持 40h，取40h的数据平均值为活性数据。在该反应中催化剂活性通过CS 2的转化率来表示，其中： 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+). 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转化率＝(进气中CS 2浓度-出气中剩余CS 2浓度)/进气中CS 2浓度*100％。 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%.
表1催化剂活性评价的结果，转化率单位为％。Table 1 Catalyst activity evaluation results, conversion rate unit is %.
Figure PCTCN2022103875-appb-000001
Figure PCTCN2022103875-appb-000001
Figure PCTCN2022103875-appb-000002
Figure PCTCN2022103875-appb-000002
从表1结果可以看出，本发明方法所制备钙钛矿型复合氧化物催化剂的水解活性优异，具备高效处理克劳斯工艺中有机硫的能力。It can be seen from the results in Table 1 that 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.

Claims (6)

  1. 一种适用于克劳斯工艺的有机硫水解催化剂，其特征在于：该催化剂的通式为：ABO x，其中A＝Na、K、Cs、Mg、Ca、Sr或Ba中的一种，B＝Ti、Fe或Co中的一种，x＝1.5-3。 An organosulfur hydrolysis catalyst suitable for the Claus process is characterized in that: the general formula of the catalyst is: ABO x , wherein A=one of Na, K, Cs, Mg, Ca, Sr or Ba, and B =One of Ti, Fe or Co, x=1.5-3.
  2. 一种权利要求1所述的适用于克劳斯工艺的有机硫水解催化剂的制备方法，其特征在于：包括以下步骤：A method for preparing an organosulfur hydrolysis catalyst applicable to the Claus process according to claim 1, characterized in that: comprising the steps of:
    (1)将金属A的前驱体溶于水中，形成含金属A的水溶液；(1) dissolving the precursor of metal A in water to form an aqueous solution containing metal A;
    (2)在剧烈搅拌条件下，将金属B的前驱体加入到步骤(1)所得的水溶液中；(2) under vigorous stirring conditions, the precursor of metal B is added to the aqueous solution obtained in step (1);
    (3)将碱金属化合物加入到步骤(2)所得的水溶液中；(3) adding the alkali metal compound to the aqueous solution obtained in step (2);
    (4)将步骤(3)所得水溶液搅拌0.5-3小时后移入水热反应釜中，100-200℃下保持12-48小时；(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;
    (5)将步骤(4)所得水溶液离心、洗涤后，在100-150℃温度下干燥6-18小时，制得粉末；(5) 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;
    (6)将粉末在450-850℃温度下焙烧4-8小时。(6) Calcining the powder at a temperature of 450-850° C. for 4-8 hours.
  3. 根据权利要求2所述的适用于克劳斯工艺的有机硫水解催化剂的制备方法，其特征在于：金属A的前驱体为金属A的硝酸盐、碳酸盐或乙酸盐。The method for preparing an organosulfur hydrolysis catalyst suitable for Claus process according to claim 2, characterized in that: the precursor of metal A is metal A nitrate, carbonate or acetate.
  4. 根据权利要求2所述的适用于克劳斯工艺的有机硫水解催化剂的制备方法，其特征在于：金属B的前驱体分为金属Ti的前驱体和金属Fe、Co的前驱体，金属Ti的前驱体为钛酸四异丙酯或钛酸四丁酯，金属Fe、Co的前驱体为Fe、Co的硝酸盐、碳酸盐或乙酸盐。According to the preparation method of the organosulfur hydrolysis catalyst applicable to the Claus process according to claim 2, it is characterized in that: 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 The precursor is tetraisopropyl titanate or tetrabutyl titanate, and the precursors of metal Fe and Co are nitrates, carbonates or acetates of Fe and Co.
  5. 根据权利要求2所述的适用于克劳斯工艺的有机硫水解催化剂的制备方法，其特征在于：碱金属化合物是NaOH、KOH、Na 2CO 3或K 2CO 3中的一种或几种。 The method for preparing an organosulfur hydrolysis catalyst suitable for the Claus process according to claim 2, wherein the alkali metal compound is one or more of NaOH, KOH, Na2CO3 or K2CO3 .
  6. 一种权利要求1所述的适用于克劳斯工艺的有机硫水解催化剂的应用，其特征在于：用于克劳斯工艺有机硫的催化水解过程中，其中：COS浓度为10～10000ppm，CS 2浓度为10～10000ppm，H 2S浓度为0～20000ppm，SO 2浓度为0～10000ppm，反应温度为180～320℃，空速为1000～10000h -1。 An application of an organosulfur hydrolysis catalyst applicable to the Claus process according to claim 1, characterized in that it is used in the catalytic hydrolysis process of the Claus process organosulfur, wherein: the COS concentration is 10 to 10000ppm, and the CS 2 The 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 .
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