CN111468158A - High-efficiency hydrogen sulfide selective oxidation catalyst and preparation method thereof - Google Patents
High-efficiency hydrogen sulfide selective oxidation catalyst and preparation method thereof Download PDFInfo
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Abstract
A preparation method of a hydrogen sulfide selective oxidation catalyst. Which comprises the following steps: mixing and grinding graphite-phase carbon nitride, metal (cobalt, iron and the like) salt and sugar, and then annealing in an inert atmosphere to prepare the carbon-coated cobalt nanoparticle catalyst. The catalyst prepared by the method does not need any pretreatment, has simple synthesis process and short production period, and can realize expanded production. The invention uses the carbon-coated metal particle catalyst for selective oxidation reaction of hydrogen sulfide for the first time. The catalyst has large specific surface area, can reach 100 percent of hydrogen sulfide conversion rate at lower temperature and can last for 28 hours, and has high stability and obvious effect.
Description
Technical Field
The invention relates to a preparation method of a high-efficiency hydrogen sulfide selective oxidation catalyst, belonging to the technical field of catalyst synthesis.
Background
With the continuous improvement of the industrial level, the national economy is improved and a series of environmental pollution problems are caused. And hydrogen sulfide (H)2S) generally comes from different industrial processes, is a gas with high toxicity, is toxic to human bodies, and can cause environmental damage. There is a strong need to develop corresponding technologies to solve this problem.
At present, there are three main hydrogen sulfide removal technologies, including a low-temperature claus reaction process, reduction absorption, and selective oxidation of hydrogen sulfide, wherein the hydrogen sulfide selective catalyst is mainly a metal oxide based catalyst (metal oxide, supported oxide, etc.), and a carbon based catalyst. Among them, the metal oxide is the most widely used catalyst in industry, has relatively high conversion efficiency and selectivity, is suitable for continuous reaction, and has high space velocity. However, metals tend to form metal-sulfur bonds with the sulfur element in hydrogen sulfide, resulting in reduced stability of the metal oxide. The development of a desulfurization catalyst with high hydrogen sulfide conversion efficiency and high stability has become a research hotspot.
The commonly used carbon-based desulfurization catalyst mainly comprises activated carbon, carbon nano tubes, carbon nano fibers and the like. The active carbon has rich micropores, large specific surface, high pore volume, rich surface acidity and alkalinity and good modifiability, and can physically adsorb hydrogen sulfide into the micropore channels, and the hydrogen sulfide is dissociated into hydrogen sulfide radicals and is further oxidized into sulfur in the presence of oxygen. However, sulfur formed in this process is directly deposited in the micropores, and the catalyst is deactivated. Nitrogen doping can regulate and control the surface acidity and alkalinity of the carbon material and improve the conversion rate of the carbon catalyst, but the stability of the nitrogen-doped carbon material needs to be improved urgently.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a high-efficiency hydrogen sulfide selective oxidation catalyst. The catalyst has a unique carbon-coated metal particle structure, overcomes the problems of complex preparation process, agglomeration, low utilization rate, easy poisoning and the like of the traditional carbon-based material catalyst, and has the advantages of high conversion efficiency, high stability and the like.
In order to achieve the purpose, the invention provides a preparation method of a high-efficiency hydrogen sulfide selective oxidation catalyst, which is used for preparing the hydrogen sulfide selective oxidation catalyst through high-temperature annealing treatment. The method comprises the following steps:
1) weighing a certain mass of carbon nitride precursor, placing the carbon nitride precursor into an alumina crucible, placing the crucible into a muffle furnace, setting a temperature-raising program, carrying out annealing treatment, and taking out graphite-phase carbon nitride (yellow solid) when the temperature of the muffle furnace naturally drops to room temperature;
2) weighing a certain mass of metal salt, sugar and the graphite-phase carbon nitride obtained in the step 1), and mixing the metal salt, the sugar and the graphite-phase carbon nitride with the following ratio (1-10): (1-10): (1-10) mixing and grinding the raw materials in a mass ratio to obtain a powdery mixture;
3) placing the powdery mixture in the step 2) in a tube furnace, vacuumizing, introducing inert gas, and repeating the operation for three times. Setting a temperature-raising program, annealing in an inert gas atmosphere, and finally grinding the product to prepare the carbon-coated metal nanoparticle catalyst.
The preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst comprises the following steps of preparing a carbon nitride precursor, and carrying out oxidation reaction on the carbon nitride precursor.
The preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst comprises the steps of preparing a metal salt, wherein the metal salt comprises metal halide, metal nitrate, metal sulfate, alkali metal salt, nitrite, carbonate, phosphate, borate and the like, the metal comprises at least one element of iron, nickel, copper, cobalt, magnesium, aluminum, manganese and the like, and preferably at least one element of cobalt nitrate, iron nitrate, cobalt chloride, iron chloride and the like.
The preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst comprises the following steps of mixing the hydrogen sulfide with the glucose, and carrying out selective oxidation on the hydrogen sulfide.
The preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst comprises the following steps of 1), wherein the heating rate is 2-10 ℃/min, the annealing temperature is preferably 450-550 ℃, and the heat preservation time is preferably 30-240 min.
The preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst, disclosed by the invention, has the advantage that the mixing and grinding time of the step 2) is 10-300 min.
The preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst comprises the following steps of 3), wherein the heating rate is 2-10 ℃/min, the annealing temperature is 500-1000 ℃, the flow rate of inert gas is 10-200m L/min, and the heat preservation duration is preferably 30-240 min.
The invention also provides a catalyst prepared by the preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst.
Advantageous effects of the invention
1) In order to be widely applied to selective oxidation of hydrogen sulfide, the selected metal source, carbon source and nitrogen source are commercial products with relatively low price. Therefore, the raw materials of the invention are cheap and easy to obtain, and the invention has commercial advantages.
2) The catalyst prepared by the invention has a unique nitrogen-doped carbon-coated metal nanoparticle structure, so that the catalyst has unique electron distribution, and the selective oxidation performance and stability of hydrogen sulfide of the catalyst are improved.
2) In the preparation method, the hydrogen sulfide selective oxidation catalyst can be obtained by only two steps. Wherein, the first step is to prepare a graphite phase carbon nitride precursor through annealing treatment; and the second step is to anneal the mixture of the metal salt, the carbon source and the graphite phase carbon nitride to finally obtain the required catalyst. Therefore, compared with the traditional related catalyst, the invention has the advantage of simple synthesis.
3) The catalyst prepared by the invention has high hydrogen sulfide selective oxidation efficiency, high desulfurization efficiency and long continuous desulfurization time. Partial catalyst can realize hydrogen sulfide conversion rate close to 100% at 190 ℃. The hydrogen sulfide conversion rate is still 91.2% at 250 ℃; meanwhile, the catalyst has high stability, and the hydrogen sulfide conversion rate of the catalyst is close to 100% after 28 hours at 190 ℃.
Drawings
FIG. 1 is a transmission electron micrograph of the catalyst prepared in example 2
FIG. 2 is an X-ray diffraction pattern of the catalyst prepared in example 2
FIG. 3 is a Raman spectrum of the catalyst prepared in example 3
FIG. 4 is a stability curve for selective catalytic oxidation of hydrogen sulfide for the catalyst prepared in example 4
Detailed Description
The present invention is further illustrated in the following specific embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed implementation procedures are given, but the protection scope of the present invention is not limited to the following implementation examples, and the experimental operations without specific conditions in the following implementation examples are generally conventional conditions.
Example 1
The invention provides a preparation method of a high-efficiency hydrogen sulfide selective oxidation catalyst, which specifically comprises the following steps:
1) weighing a certain mass of carbon nitride precursor, placing the carbon nitride precursor into an alumina crucible, placing the crucible into a muffle furnace, setting a temperature-raising program, raising the temperature to 550 ℃ at a temperature-raising rate of 10 ℃/min, preserving the temperature for 30min, and taking out graphite-phase carbon nitride (yellow solid) when the temperature of the muffle furnace naturally drops to room temperature;
2) weighing 100mg of ferric nitrate, 300mg of glucose and 100mg of the graphite-phase carbon nitride obtained in the step 1), mixing and grinding the three components for 30min to obtain mixed powder;
3) placing the mixed powder in the step 2) in a tubular furnace, vacuumizing, introducing nitrogen, repeating the operation for three times, setting a heating program, heating to 600 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 30min, naturally cooling to room temperature, and grinding the product to prepare the carbon-coated iron nanoparticle catalyst.
In a fixed quartz bed reactor, 50mg of the catalyst is taken in a mixed gas of 0.5 percent of hydrogen sulfide, 0.25 percent of oxygen and 99.25 percent of helium, the reaction temperature is 100 ℃ and 250 ℃, and the sulfur yield and the like of the catalyst are tested when the mass space velocity is 18000m L/(g.h).
The result shows that the sulfur yield of the catalyst at 250 ℃ reaches the highest and is 86.2 percent
Example 2
1) Weighing a certain mass of carbon nitride precursor, placing the carbon nitride precursor into an alumina crucible, placing the crucible into a muffle furnace, setting a temperature-raising program, raising the temperature to 550 ℃ at a temperature-raising rate of 10 ℃/min, preserving the temperature for 30min, and taking out graphite-phase carbon nitride (yellow solid) when the temperature of the muffle furnace naturally drops to room temperature;
2) weighing 200mg of cobalt nitrate, 300mg of glucose and 100mg of graphite-phase carbon nitride obtained in the step 1), mixing and grinding the cobalt nitrate, the glucose and the graphite-phase carbon nitride for 30min to obtain mixed powder;
3) and (3) placing the mixed powder in the step (2) in a tubular furnace, vacuumizing, introducing nitrogen, repeating the operation for three times, setting a heating program, heating to 600 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 30min, naturally cooling to room temperature, and grinding the product to prepare the carbon-coated cobalt nanoparticle catalyst.
In a fixed quartz bed reactor, 50mg of the catalyst is taken in a mixed gas of 0.5 percent of hydrogen sulfide, 0.25 percent of oxygen and 99.25 percent of helium, the reaction temperature is 100 ℃ and 250 ℃, and the sulfur yield and the like of the catalyst are tested when the mass space velocity is 18000m L/(g.h).
The result shows that the sulfur yield of the catalyst at 220 ℃ reaches the highest and is 94 percent
Example 3
1) Weighing a certain mass of carbon nitride precursor, placing the carbon nitride precursor into an alumina crucible, placing the crucible into a muffle furnace, setting a temperature-raising program, raising the temperature to 550 ℃ at a temperature-raising rate of 10 ℃/min, preserving the temperature for 30min, and taking out graphite-phase carbon nitride (yellow solid) when the temperature of the muffle furnace naturally drops to room temperature;
2) weighing 500mg of cobalt nitrate, 300mg of glucose and 100mg of graphite-phase carbon nitride obtained in the step 1), mixing and grinding the cobalt nitrate, the glucose and the graphite-phase carbon nitride for 30min to obtain mixed powder;
3) and (3) placing the mixed powder in the step (2) in a tubular furnace, vacuumizing, introducing nitrogen, repeating the operation for three times, setting a heating program, heating to 600 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 30min, naturally cooling to room temperature, and grinding the product to prepare the carbon-coated cobalt nanoparticle catalyst.
In a fixed quartz bed reactor, 50mg of the catalyst is taken in a mixed gas of 0.5 percent of hydrogen sulfide, 0.25 percent of oxygen and 99.25 percent of helium, the reaction temperature is 100 ℃ and 250 ℃, and the sulfur yield and the like of the catalyst are tested when the mass space velocity is 18000m L/(g.h).
The result shows that the sulfur yield of the catalyst at 220 ℃ reaches the highest and is 92.7 percent
Example 4
1) Weighing a certain mass of carbon nitride precursor, placing the carbon nitride precursor into an alumina crucible, placing the crucible into a muffle furnace, setting a temperature-raising program, raising the temperature to 550 ℃ at a temperature-raising rate of 10 ℃/min, preserving the temperature for 30min, and taking out graphite-phase carbon nitride (yellow solid) when the temperature of the muffle furnace naturally drops to room temperature;
2) weighing 200mg of cobalt nitrate, 400mg of glucose and 100mg of graphite-phase carbon nitride obtained in the step 1), mixing and grinding the cobalt nitrate, the glucose and the graphite-phase carbon nitride for 30min to obtain mixed powder;
3) and (3) placing the mixed powder in the step (2) in a tubular furnace, vacuumizing, introducing nitrogen, repeating the operation for three times, setting a heating program, heating to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 30min, naturally cooling to room temperature, and grinding a product to prepare the carbon-coated cobalt nanoparticle catalyst.
In a fixed quartz bed reactor, 50mg of catalyst is taken to be in a mixed gas of 0.5 percent of hydrogen sulfide, 0.25 percent of oxygen and 99.25 percent of helium, the reaction temperature is 100 ℃ and 250 ℃, and the desulfurization performance of the catalyst is tested when the mass space velocity is 18000m L/(g.h).
The results show that the sulfur yield of the catalyst reaches the highest value of 97.2% at 190 ℃.
The above embodiments are merely examples for clearly illustrating the present invention and are not intended to limit the scope of the present invention. Other variations and modifications may be made on the basis of the foregoing description, and it is to be understood that such variations and modifications are obvious and fall within the scope of the invention as claimed.
Claims (9)
1. The preparation method of the high-efficiency hydrogen sulfide selective oxidation catalyst is prepared by mixing, grinding and annealing carbon nitride, sugar and metal salt, and comprises the following specific steps:
1) weighing a certain mass of carbon nitride precursor, placing the carbon nitride precursor into an alumina crucible, placing the crucible into a muffle furnace, setting a temperature-raising program, carrying out annealing treatment, and taking out graphite-phase carbon nitride (yellow solid) when the temperature of the muffle furnace naturally drops to room temperature;
2) weighing a certain mass of metal salt, saccharides and the graphite-phase carbon nitride obtained in the step 1), and mixing and grinding the metal salt, the saccharides and the graphite-phase carbon nitride to obtain a powdery mixture;
3) and (3) placing the powdery mixture in the step (2) in a tubular furnace, and annealing in an inert gas atmosphere to prepare the carbon-coated metal nanoparticle catalyst.
2. The method according to claim 1, wherein the carbon nitride precursor is selected from dicyanodiamine, melamine, urea, etc., preferably melamine; the heating rate is 2-10 ℃/min, the annealing temperature is 450-.
3. The process according to claim 1, wherein the catalyst is used for selective oxidation of hydrogen sulfide for desulfurization.
4. The method according to claim 1, wherein the metal salt is selected from the group consisting of metal halides, metal nitrates, metal sulfates, alkali metal salts, nitrites, carbonates, phosphates, borates, and the like, and the metal salt is selected from the group consisting of at least one element selected from the group consisting of iron, nickel, copper, cobalt, magnesium, aluminum, manganese, and the like, and preferably at least one element selected from the group consisting of cobalt nitrate, iron nitrate, cobalt chloride, and iron chloride.
5. The process according to claim 1, wherein the sugar is at least one of glucose, a disaccharide and a polysaccharide.
6. The method of claim 1, wherein the resulting catalyst structure is a carbon-coated metal nanoparticle.
7. The method according to claim 1, wherein the mass ratio of the metal salt, the carbon nitride and the sugar is (1-10): (1-10): (1-10).
8. The method as claimed in claim 1, wherein the annealing temperature of the powdered mixture is 500-1000 ℃ and the holding time is 30-240 min.
9. The preparation method according to claim 1, wherein the obtained carbon-coated metal nanoparticle catalyst has high hydrogen sulfide catalytic activity, high selectivity and high stability.
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