CN114558566B - Hydrogen sulfide selective oxidation catalyst and preparation method and application thereof - Google Patents

Hydrogen sulfide selective oxidation catalyst and preparation method and application thereof Download PDF

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CN114558566B
CN114558566B CN202210239764.0A CN202210239764A CN114558566B CN 114558566 B CN114558566 B CN 114558566B CN 202210239764 A CN202210239764 A CN 202210239764A CN 114558566 B CN114558566 B CN 114558566B
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manganese dioxide
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CN114558566A (en
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肖益鸿
郑程程
杨勤丰
郑勇
曹彦宁
刘福建
江莉龙
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Fuzhou University
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Abstract

The invention belongs to the technical field of material preparation and environmental catalysis, and particularly relates to a hydrogen sulfide selective oxidation catalyst, and a preparation method and application thereof. Catalyst cerium manganese composite metal oxide (Ce-MnO) 2 ) Through KMnO 4 Adding cerium salt and reducing precipitant to react. Slowly adding a reducing precipitant into an aqueous solution of which the potassium permanganate and the cerium salt are uniformly mixed, and stirring, hydrothermal, separating, drying and roasting to obtain the cerium modified manganese dioxide catalyst. The cerium modified manganese dioxide catalyst prepared by the method provided by the invention has large specific surface area and is applied to H 2 S shows high H in the selective catalytic oxidation reaction 2 S conversion rate and sulfur selectivity, and has better stability.

Description

Hydrogen sulfide selective oxidation catalyst and preparation method and application thereof
Technical Field
The invention relates to a preparation technology of an environmental catalyst and the application field thereof, in particular to a preparation method of a hydrogen sulfide selective oxidation catalyst and application thereofH 2 Application of S in selective catalytic oxidation.
Background
Process for desulfurizing gasoline or diesel oil in the petroleum industry, comprising a large amount of hydrogen sulfide (H 2 S) refining process of natural gas and methane, and melting process of metal in steel production are often accompanied by considerable content of H 2 S is generated. With the continuous development and progress of society, people are increasingly focusing on the problems of environmental pollution and resource recycling. Claus process for H removal 2 S and sulfur recovery are the most commonly used desulfurization process with the largest standard. However, the thermodynamic equilibrium limits, 2% to 5% of H remains in the exhaust gas 2 S, S. To further remove residual H 2 S, various additional purification methods have been developed. Wherein H is 2 S-Selective Catalytic Oxidation (SCO) has attracted extensive research interest in the last decades. It can directly and completely convert H 2 S is converted to elemental sulfur. However, undesirable side reactions produce SO 2 The sulfur yield is reduced. The SCO main reaction is shown as a formula (1), and the side reactions are shown as a formula (2) and a formula (3).
In the reaction, SO 2 Can pass through H 2 S is deeply oxidized or S is further oxidized to form, resulting in a decrease in sulfur yield. Thus, the yield of sulfur is largely dependent on the catalytic performance of the catalyst. Therefore, the development of low cost, high activity, high selectivity and excellent durability catalysts remains H 2 S selective catalytic oxidation is an urgent problem to be solved.
At present, the most studied of the hydrogen sulfide selective oxidation catalyst systems are a carbon material system and a metal oxide system, and the pillared clay system has better activity, but the stability is still to be examined. The carbon material has abundant porosity, high specific surface area, and acidic/basic surface properties that can be easily modified, and can serve as a catalyst or catalyst support. The carbon material itself is used as a catalyst, and has a usable space velocityDisadvantages of low and poor selectivity; it acts as a carrier, the activity of which depends on the active substance being highly dispersed on the surface, but the active substance is easily lost. Metal oxides have been considered as catalysts for this reaction, mainly comprising Fe 2 O 3 、TiO 2 、V 2 O 5 And CeO 2 Etc. Iron oxide as catalyst in H 2 The S selective oxidation process is widely studied. The pure iron oxide catalyst has low activity, good conversion rate under the condition of peroxy, low sulfur selectivity under the condition of peroxy and low stability. In contrast, tiO 2 More active, selective and stable at high temperature, is used as H 2 A powerful competitor for S-selective oxidation catalysts, but TiO 2 There is a disadvantage in that water poisoning is easy. Vanadium is the most active substance, but its high toxicity limits its use. Notably, rare earth Ce has recently been widely studied for its excellent redox performance and high oxygen storage capacity, but has disadvantages of low activity and poor stability, and thus, development of efficient and high-stability removal of H has been made 2 The environmental protection of the catalyst for S remains a challenge.
Among the transition metal oxide catalysts, manganese oxide has attracted attention due to its unique physicochemical properties (e.g., polymorphism and non-stoichiometric composition), environmental friendliness, and low cost. Concerning Mn-based materials in H 2 The use of S in selective catalytic oxidation has been reported. However, the MnO is reported in the literature 2 The activity and stability of the materials still need to be improved. Single MnO 2 The material has low specific surface area and low electron transmission efficiency, which limits the material in H 2 S catalysis field application.
The invention utilizes cerium modified manganese dioxide and searches the cerium modified manganese dioxide catalyst in H 2 The application in the field of S selective catalytic oxidation can improve the texture property, induce the generation of oxygen vacancies, and enhance the oxidation-reduction performance and the oxygen mobility of the cerium, thereby improving the catalytic activity.
Disclosure of Invention
The present invention aims at MnO 2 The material also has low specific surface area and livingThe problem of poor performance, a preparation method and application of a cerium modified manganese dioxide catalyst are provided, and H in the prior art is solved 2 The S selective oxidation transition metal oxide catalyst has the problems of poor activity, poor stability and the like, and aims to prepare the cerium-manganese composite metal oxide catalyst with better activity and excellent stability.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
a method for preparing a hydrogen sulfide selective oxidation catalyst, comprising the following steps:
a. weighing potassium permanganate and cerium salt with a certain proportion, adding the potassium permanganate and the cerium salt into deionized water, and stirring the mixture for 10 minutes at room temperature to prepare a manganese-cerium mixed salt aqueous solution;
b. adding the weighed reducing precipitant into deionized water in another beaker, and stirring for 10min; then adding the aqueous solution of the reducing precipitant into the aqueous solution of the manganese-cerium mixed salt, and continuously stirring for 10-60min at room temperature;
c. transferring the solution obtained in the step b into a high-pressure reaction kettle for hydro-thermal treatment for 4-24 hours, naturally cooling the high-pressure kettle to room temperature after the reaction is finished, washing and filtering the precipitate by deionized water, and drying at 100 ℃ for 12 hours;
d. and (3) placing the dried sample into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min, and roasting for 3 hours to obtain the hydrogen sulfide selective oxidation catalyst.
Preferably, the molar ratio of Ce/Mn in the step a is 0.05-1, and the total molar concentration of the mixed solution of potassium permanganate and cerium salt is 0.1-0.5 mol/L.
Preferably, the cerium salt in the step a may be one or more of cerium nitrate, cerium sulfate, cerium acetate and cerium trichloride.
Preferably, the reducing precipitant in the step b is at least one of hydrogen peroxide, lactic acid and ascorbic acid; the molar concentration of the aqueous solution of the reducing precipitant is 0.1 to 0.5 mol per liter.
Preferably, the molar ratio of the reducing precipitant to the potassium permanganate in the step b is 0.1-1:1.
preferably, the hydrothermal treatment temperature in the step c is 100-180 ℃ and the reaction time is 4-24h.
The application of the hydrogen sulfide selective oxidation catalyst prepared by the preparation method comprises the following steps: for selective catalytic oxidation of H 2 S。
Preferably, the selective catalytic oxidation of H 2 In the raw material gas of S reaction, O 2 The concentration is H 2 1/2 of S concentration.
Preferably, the reaction temperature for the selective catalytic oxidation is 90 ℃ to 240 ℃.
Preferably, the cerium modified manganese dioxide catalyst loading is 0.10g; h 2 S concentration is 5000ppm, O 2 Concentration of 2500ppm, N 2 Balance the gas; the space velocity of the raw material gas is 18000 mL.g -1 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the The flow rate of the raw material gas is 30 mL/min -1 。
The invention has the following advantages and beneficial effects:
1. the invention firstly combines cerium-manganese composite metal oxide (Ce-MnO 2 ) Application in H 2 S selective catalytic oxidation field expands the application range of cerium-manganese composite metal oxide; at 18000mL g -1 ·h -1 The catalyst can be converted into near percent at 150 ℃ at the mass airspeed of (3), and has high selectivity and good stability;
2. the invention adopts a specific reduction precipitant to lead the synthesized cerium-manganese composite metal oxide to have a special lamellar structure, and the specific surface area can reach 160-300 m 2 Per gram, existing generally below 200 m 2 And/g. The large specific surface area facilitates the contact of reactants with the active sites of the catalyst, thereby facilitating the selective catalytic oxidation of H 2 The activity of S is enhanced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the catalyst prepared in example 1 (A) and example 3 (B);
FIG. 2 shows the catalysts prepared in examples 1 to 4 and comparative examples 1 and 2 at H 2 H in S selective catalytic oxidation reaction 2 S conversion curve graph;
FIG. 3 shows the catalysts prepared in examples 1 to 4 and comparative examples 1 and 2 at H 2 H in S selective catalytic oxidation reaction 2 S selectivity graph;
FIG. 4 shows the catalysts prepared in examples 1 to 4 and comparative examples 1 and 2 at H 2 H in S selective catalytic oxidation reaction 2 S yield graph;
FIG. 5 shows the catalyst prepared in example 3 at H 2 Stability profile in S selective catalytic oxidation reactions.
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples.
Example 1
0.01mol of potassium permanganate and 0.5mmol of cerium nitrate hexahydrate were weighed into 60mL of deionized water and stirred at room temperature for 10 minutes. Then, the weighed amount of 0.001mol of ascorbic acid was added to 10mL of deionized water, and stirred at room temperature for 10 minutes. Then adding the aqueous solution of the reducing precipitant into the mixed solution of potassium permanganate and cerium nitrate hexahydrate, and stirring for 10 minutes at room temperature. Then transferring the solution into a 100mL autoclave for hydrothermal treatment at 100 ℃ for 24, naturally cooling the autoclave to room temperature after the reaction is finished, washing and filtering the precipitate by deionized water, and drying at 100 ℃ for 12 hours. Then the mixture is heated to 300 ℃ at a heating rate of 3 ℃/min and baked for 3 hours to obtain the cerium modified manganese dioxide catalyst which is named as 5Ce-MnO 2 。
Example 2
0.01mol of potassium permanganate and 0.001mol of cerium nitrate hexahydrate were weighed into 60mL of deionized water, and stirred at room temperature for 10 minutes. Then, the weighed amount of 0.001mol of ascorbic acid was added to 10mL of deionized water, and stirred at room temperature for 10 minutes. Then the reducing precipitant is dissolved in waterThe solution was added to a mixed solution of potassium permanganate and cerium nitrate hexahydrate, and stirring was continued at room temperature for 10 minutes. Then transferring the solution into a 100mL autoclave for hydrothermal treatment at 100 ℃ for 24, naturally cooling the autoclave to room temperature after the reaction is finished, washing and filtering the precipitate by deionized water, and drying at 100 ℃ for 12 hours. Then the mixture is heated to 300 ℃ at a heating rate of 3 ℃/min and baked for 3 hours to obtain the cerium modified manganese dioxide catalyst which is named as 10Ce-MnO 2 。
Example 3
0.01mol of potassium permanganate and 0.005mol of cerium nitrate hexahydrate were weighed into 60mL of deionized water, and stirred at room temperature for 10 minutes. Then, the weighed amount of 0.001mol of ascorbic acid was added to 10mL of deionized water, and stirred at room temperature for 10 minutes. Then adding the aqueous solution of the reducing precipitant into the mixed solution of potassium permanganate and cerium nitrate hexahydrate, and stirring for 10 minutes at room temperature. Then transferring the solution into a 100mL autoclave for hydrothermal treatment at 100 ℃ for 24, naturally cooling the autoclave to room temperature after the reaction is finished, washing and filtering the precipitate by deionized water, and drying at 100 ℃ for 12 hours. Then the mixture is heated to 300 ℃ at a heating rate of 3 ℃/min and baked for 3 hours to obtain the cerium modified manganese dioxide catalyst which is named as 50Ce-MnO 2 。
Example 4
0.01mol of potassium permanganate and 0.01mol of cerium nitrate hexahydrate were weighed into 60mL of deionized water, and stirred at room temperature for 10 minutes. Then, the weighed amount of 0.001mol of ascorbic acid was added to 10mL of deionized water, and stirred at room temperature for 10 minutes. Then adding the aqueous solution of the reducing precipitant into the mixed solution of potassium permanganate and cerium nitrate hexahydrate, and stirring for 10 minutes at room temperature. Then transferring the solution into a 100mL autoclave for hydrothermal treatment at 100 ℃ for 24, naturally cooling the autoclave to room temperature after the reaction is finished, washing and filtering the precipitate by deionized water, and drying at 100 ℃ for 12 hours. Then the mixture is heated to 300 ℃ at a heating rate of 3 ℃/min and baked for 3 hours to obtain the cerium modified manganese dioxide catalyst which is named as 100Ce-MnO 2 。
Comparative example 1
0.01mol of potassium permanganate was weighed, added to 60mL of deionized water, and stirred at room temperature for 10min.Then, the weighed amount of 0.001mol of ascorbic acid was added to 10mL of deionized water, and stirred at room temperature for 10 minutes. Then adding the aqueous solution of the reducing precipitant into the potassium permanganate solution, and stirring for 10min at room temperature. Then transferring the solution into a 100mL autoclave for hydrothermal treatment at 100 ℃ for 24, naturally cooling the autoclave to room temperature after the reaction is finished, washing and filtering the precipitate by deionized water, and drying at 100 ℃ for 12 hours. Then the temperature is raised to 300 ℃ at the heating rate of 3 ℃/min for roasting for 3 hours to obtain the manganese dioxide catalyst which is named as 0Ce-MnO 2 。
Comparative example 2
0.01mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in 30mL deionized water and stirred for 30min. An 8wt% ammonia solution was then gradually dropped into the solution with stirring to maintain the pH at 10. After stirring for a further 30 minutes, the solution was treated in an autoclave at 150℃for 24 hours. After the reaction is completed, the autoclave is naturally cooled to room temperature, and the precipitate is washed and filtered by deionized water and baked at 100 ℃ for 12 hours. Then the mixture is heated to 500 ℃ at a heating rate of 3 ℃/min and baked for 3 hours to obtain the cerium oxide catalyst named CeO 2 。
Fig. 1 is an SEM image of the cerium-manganese composite metal oxide prepared in examples 1 and 3 of the present invention. As shown in FIG. 1 (A), at a low cerium modification ratio, the 5Ce-Mn catalyst was entangled with nanorods having an average size of 10.2nm, and arranged in agglomerates having different sizes. As shown in (B) of fig. 1, the 50Ce-Mn prepared in example 3 has a remarkable lamellar structure, and may be a material structure in which high concentration of cerium ions is introduced under the action of a reducing precipitant to greatly destroy manganese dioxide, so that it exhibits a morphological feature different from that of low cerium modification ratio.
The texture properties of the catalysts prepared in examples 1 to 4 and comparative example 1 of the present invention are shown in Table 1. As is clear from Table 1, the specific surface area of the sample was 10Ce-MnO 2 >50Ce-MnO 2 >5Ce-MnO 2 >100Ce-MnO 2 >0Ce-MnO 2 In which 10Ce-MnO 2 The specific surface area of (a) reaches 250.6 m 2 /g，50Ce-MnO 2 And 100Ce-MnO 2 The specific surface area of the sample was slightly reduced. Sample ratio meterThe area, the mesoporous volume and the mesoporous aperture all show a rule of increasing and then decreasing with the increase of the Ce content, wherein 10Ce-MnO 2 Is the maximum of (a). Notably, the pore size of the micropores gradually decreases with increasing cerium, 50Ce-MnO 2 And 100Ce-MnO 2 The micropores disappear. 50Ce-MnO 2 The mesoporous material has high mesoporous rate and large specific surface area, is favorable for gaseous reactants to enter active sites, and the product sulfur is easy to desorb, thereby having higher H 2 S conversion and stability.
TABLE 1 texture Properties of the catalysts prepared in examples 1 to 4 and comparative example 1 of the present invention
Selective catalytic oxidation of H 2 S performance test: the catalysts prepared in the above examples and comparative examples were crushed and sieved into 30-80 mesh particles for H 2 Evaluation of the selective catalytic oxidation activity of S. The test conditions were as follows: catalyst loading was 0.10g, feed gas was varied from 5000ppm H 2 S、2500 ppm O 2 And balance gas nitrogen, the flow rate of the raw material gas is 30mL min -1 The space velocity (GHSV) of the raw material gas is 18000 mL.g -1· h -1 The reaction temperature is 90-240 ℃, and the raw material gas is three-component gas (5000 ppm,2500ppm, N) 2 Balance gas).
The catalysts prepared in each example and comparative example were applied to H 2 S selective catalytic oxidation reaction, H thereof 2 The S conversion, sulfur selectivity and sulfur yield were calculated as follows:
FIG. 2 shows the selective catalytic oxidation of H in the temperature range of 90-240 ℃ for the catalysts prepared in examples 1-4 and comparative examples 1-2 of the present invention 2 S conversion plot. H 2 The S conversion increases as the reaction temperature increases from 90 ℃ to 240 ℃. Furthermore, when the Ce/Mn molar ratio is increased from 0% to 5At 0%, H 2 The S conversion is significantly increased. 50Ce-MnO 2 The samples showed the highest conversion, H at 150 ℃C 2 S can reach 100% conversion. When the Ce/Mn molar ratio reaches 100%, H 2 The S conversion is instead reduced and only 100% conversion is achieved at 210 ℃. Overall, ce content vs H 2 The S conversion effect is very pronounced. Notably, all Ce-MnO, although there was a difference in activity of the modified samples with different Ce contents 2 The sample can realize complete H at 210 DEG C 2 S conversion, shows a ratio of 0Ce-MnO under the same reaction conditions 2 And CeO 2 Higher H 2 S conversion.
FIG. 3 shows the selective catalytic oxidation of H in the temperature range of 90-240 ℃ for the catalysts prepared in examples 1-4 and comparative examples 1-2 of the present invention 2 Sulfur selectivity profile for S. It is evident that the selectivity of sulfur remains constant at 100% at 150 ℃ and below for all samples. With further increase of temperature, ceO 2 、0Ce-MnO 2 、5Ce-MnO 2 And 10Ce-MnO 2 Selectivity of (2) is lowered by 50Ce-MnO 2 And 100Ce-MnO 2 100% was also maintained at 180 ℃ and the selectivity dropped slowly throughout the temperature range. Overall, the change in sulfur selectivity exhibited CeO 2 < 5Ce-MnO 2 < 10Ce-MnO 2 < 0Ce-MnO 2 < 50Ce-MnO 2 < 100Ce-MnO 2 Trend of (3).
FIG. 4 shows the selective catalytic oxidation of H in the temperature range of 90-240 ℃ for the catalysts prepared in examples 1-4 and comparative examples 1-2 of the present invention 2 Sulfur yield profile for S. xCe-MnO when the temperature is lower than 150 DEG C 2 Trend of variation of sulfur yield and H of sample 2 The S conversion is similar because there is less reduction in selectivity to sulfur. With further increases in temperature, the sulfur yield of all samples decreased at higher temperatures, as the sulfur selectivity slowly decreased. Wherein, 50Ce-MnO 2 A sulfur yield of 100% can be achieved at 150 c, which is higher than most catalysts currently.
FIG. 5 is a graph showing the reaction temperature of 180℃for the catalyst prepared in example 3 of the present invention) Stability profile at time. Specifically, 50Ce-MnO 2 The catalyst showed nearly 100% H over the first 24 hours 2 S conversion, then H 2 The S conversion was slightly reduced but H at 50H 2 The S conversion is still greater than 90%. In addition, 50Ce-MnO 2 The selectivity does not change much during the test time.
In conclusion, the cerium-manganese composite metal oxide prepared by the invention is characterized in that 2 The S has excellent performance in the selective catalytic oxidation reaction, high stability and great application potential.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent changes and modifications made in the claims shall fall within the scope of the present invention.

Claims (3)

1. The application of the cerium modified manganese dioxide catalyst is characterized in that: the cerium modified manganese dioxide catalyst is used for selective catalytic oxidation of H 2 S；
The preparation method of the cerium modified manganese dioxide catalyst comprises the following steps:
weighing 0.01mol of potassium permanganate and 0.005mol of cerium nitrate hexahydrate, adding into 60mL of deionized water, and stirring at room temperature for 10min; then adding the weighed 0.001mol of ascorbic acid into 10mL of deionized water, and stirring for 10min at room temperature; then adding the ascorbic acid aqueous solution into the mixed solution of potassium permanganate and cerium nitrate hexahydrate, and continuously stirring for 10 minutes at room temperature; transferring the solution into a 100mL autoclave for hydrothermal treatment at 100 ℃ for 24, naturally cooling the autoclave to room temperature after the reaction is finished, washing and filtering the precipitate with deionized water, baking at 100 ℃ for 12 hours, and then heating to 300 ℃ at a heating rate of 3 ℃/min for 3 hours to obtain the cerium-modified manganese dioxide catalyst.
2. The use according to claim 1, characterized in that: for selective catalytic oxidation of H 2 In the S process, the reaction temperature is 90-240 ℃.
3. The use according to claim 1, characterized in that: the catalyst was used in an amount of 0.10g; the granularity of the catalyst is 30-80 meshes; the raw material gas comprises the following components in sequence: 5000ppmH 2 S and 2500ppmO 2 ，N 2 Is balance gas; the reaction space velocity is 18000 mL.g -1 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the The flow rate of the raw material gas is 30 mL/min -1 。
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