CN109985654B - Alkali metal ion modified carbon nitride catalyst and preparation method and application thereof - Google Patents
Alkali metal ion modified carbon nitride catalyst and preparation method and application thereof Download PDFInfo
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- CN109985654B CN109985654B CN201910341462.2A CN201910341462A CN109985654B CN 109985654 B CN109985654 B CN 109985654B CN 201910341462 A CN201910341462 A CN 201910341462A CN 109985654 B CN109985654 B CN 109985654B
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to an alkali metal ion modified carbon nitride catalyst, and a preparation method and application thereof. The catalyst takes carbon nitride as a main body, and the modified alkali metal ions comprise Na+、K+And Cs+One or a combination of more of them, wherein the content of alkali metal ions is 0.1-10 wt%; the alkali metal ions in the catalyst adsorb on the deprotonated amino nitrogen of the carbon nitride by electrostatic interaction. The catalyst of the invention can be used as an organic sulfur hydrolysis catalyst and shows good catalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an alkali metal ion modified carbon nitride catalyst, and a preparation method and application thereof.
Background
Carbonyl sulfide (COS) is a major form of organic sulfur, and is widely present in fossil raw materials such as coal, natural gas, and petroleum. Trace COS in industrial production easily causes catalyst poisoning and inactivation in production procedures, corrosion of production equipment and instruments and influences the quality of chemical products; in addition, the untreated COS is released to the atmosphere and reacts with oxygen to form SO2The photochemical reaction is promoted, which brings serious environmental pollution and threatens human health. Carbonyl sulfide is stable in physicochemical properties, weak in acidity, and H2S phase ratio is not easy to dissociate and liquefy, and is generally used for removing H2The method of S cannot completely and effectively remove COS directly. At present, the main removal technologies of COS include hydrolysis, reduction, absorption, adsorption, photolysis and oxidation, among which, the removal of COS by hydrolysis proves to be one of the most effective methods, and the basic principle is as follows: COS reacts with water under the action of catalyst to be converted into H2S, then H is removed by other methods2S, the whole process is simple to operate, and energy consumption is low. Key technology of hydrolysis methodThe technology is to develop a high-efficiency and economical catalyst.
At present, a catalyst for hydrolyzing COS is mostly prepared by using a metal oxide or activated carbon as a carrier and further loading an active component on the metal oxide or activated carbon. Most of the supported COS hydrolysis catalysts contain transition metals, and have the defects of high price, complex preparation process, easy falling of active components from carriers, poor activity stability and the like. Therefore, by innovating the COS hydrolysis catalyst, it is novel to invent a COS hydrolysis catalyst that does not contain a transition metal and has a strong interaction of an active component with a carrier.
In recent years, carbon nitride having a graphite-like structure composed of carbon and nitrogen-rich elements has received much attention. The carbon nitride polymer has good heat resistance, chemical corrosion resistance, no toxicity, low price, good biocompatibility and semiconductor properties, and has very good application prospect in the fields of energy and catalysis at present. The carbon nitride surface has abundant amino groups which are not polymerized completely, and can be used as an ideal alkali catalyst and a load type catalyst carrier. The COS hydrolysis reaction is a base catalytic reaction, and the carbon nitride modified by the alkali metal ions synthesized by the ionothermal method has strong basicity, and the alkali metal ions can be adsorbed on the carbon nitride carrier through electrostatic interaction, so that the carbon nitride carrier is not easy to fall off and has good dispersibility. Therefore, the carbon nitride modified by the alkali metal ions is expected to be a high-efficiency catalyst for hydrolyzing COS.
Jiangjing et al, in the "journal of catalysis academy of academic or vocational study" disclose a comparative study of alkali metal-doped graphite-phase carbon nitride in visible light photocatalytic hydrogen production, wherein alkali metal hydroxide is used for doping carbon nitride, but the alkali metal hydroxide has strong basicity, so that the main body structure of the graphite-phase carbon nitride and the alkali metal hydroxide is easily destroyed in the high-temperature treatment process, and the crystallinity of the graphite-phase carbon nitride is reduced. Therefore, pi is reduced in the conjugated system and is not high in basicity. In the invention, in the synthesis of the alkali metal ion modified carbon nitride by the ionothermal method, neutral alkali metal halide is used as an ionic solvent to react with the carbon nitride at high temperature, so that the crystallinity of the carbon nitride is greatly improved, and the pi conjugated system is expanded. Therefore, the synthesized alkali metal ion-modified carbon nitride has strong basicity.
Disclosure of Invention
In order to solve at least one aspect of the above problems and disadvantages of the prior art, the present invention provides an alkali metal ion-modified carbonyl sulfide hydrolysis catalyst and a method for preparing the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a carbon nitride catalyst modified by alkali metal ions in a first aspect, wherein the alkali metal ions comprise Na+、K+And Cs+One or more of them, wherein the content of alkali metal ions is 0.1-10 wt%. The alkali metal ions in the catalyst adsorb on the deprotonated amino nitrogen of the carbon nitride by electrostatic interaction.
The second aspect of the invention discloses a preparation method of the alkali metal ion modified carbon nitride catalyst, which comprises the following steps:
(1) calcining the nitrogen-containing organic compound for 2-4h at the temperature of 450-650 ℃ in the air or nitrogen atmosphere to obtain carbon nitride;
(2) grinding and uniformly mixing the carbon nitride obtained in the step (1) and alkali metal chloride;
(3) calcining the mixture obtained in the step (2) at the temperature of 650 ℃ in an inert atmosphere of 550-4 h to generate the carbon nitride modified by the alkali metal ions;
(4) and (4) mixing the solid powder obtained in the step (3) with deionized water, then filtering to remove alkali metal ions which are not adsorbed on carbon nitride, and drying the obtained solid for at least 6 hours to obtain the alkali metal ion modified carbon nitride catalyst.
The nitrogen-containing organic compound in the step (1) is one or more of cyanamide, dicyandiamide, melamine, ammonium thiocyanate, thiourea, guanidine carbonate and urea.
The alkali metal halide in the step (2) is one or more of sodium chloride, potassium chloride, cesium chloride, sodium bromide, potassium bromide and cesium bromide. The mass ratio of the carbon nitride to the alkali metal halide is as follows: 1, (0.5-50).
The third aspect of the invention discloses the application of the alkali metal ion modified carbon nitride catalyst in catalyzing and hydrolyzing COS.
The invention has the following remarkable advantages:
(1) the synthesis method is safe and environment-friendly, the preparation process is simple, and the conditions are mild and controllable.
(2) The synthesized alkali metal ion modified carbon nitride catalyst does not contain transition metal, and the raw material is cheap; the alkali metal ions are uniformly dispersed on the carbon nitride, have strong interaction with the carbon nitride and are not easy to fall off.
(3) The alkali metal ion modified carbon nitride catalyst synthesized by the method can be used for catalyzing and hydrolyzing COS reaction, the COS conversion rate reaches 92% in a 10-hour catalytic reaction (70 ℃) test, the activity is not obviously changed, and the stability is good.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (XRD) of the ionothermal-synthesized potassium ion-modified carbon nitride and the immersion-synthesized potassium ion-supported carbon nitride obtained in example 1;
FIG. 2 is an infrared (FTIR) spectrum of the ionothermal synthesized potassium ion modified carbon nitride and the impregnation synthesized potassium ion supported carbon nitride obtained in example 1;
FIG. 3 is a Transmission Electron Micrograph (TEM) and mapping of potassium ion-modified carbon nitride synthesized in example 1;
FIG. 4 is a graph showing activity of potassium ion-modified carbonitride synthesized in example 1 and potassium ion-supported carbonitride synthesized by impregnation in catalyzing hydrolysis of COS (70 ℃ C.).
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
10g of melamine was first weighed into an alumina crucible and calcined at 550 ℃ for 4h in an air atmosphere. And naturally cooling, taking out the sample, and grinding into powder to obtain the carbon nitride powder. Weighing 2g of carbon nitride powder and 10g of alkali metal chloride (potassium chloride), uniformly grinding, calcining for 2h at 600 ℃ in a nitrogen atmosphere, naturally cooling to obtain a solid, ultrasonically dispersing the solid in water, removing free potassium ions on the surface of the carbon nitride, filtering, and drying to obtain the potassium ion modified carbon nitride.
Example 2
10g of melamine was first weighed into an alumina crucible and calcined at 550 ℃ for 2h in an air atmosphere. And naturally cooling, taking out the sample, and grinding into powder to obtain the carbon nitride powder. Weighing 2g of carbon nitride powder and 10g of alkali metal chloride (sodium chloride), uniformly grinding, calcining for 2h at 600 ℃ in a nitrogen atmosphere, naturally cooling to obtain a solid, ultrasonically dispersing the solid in water, removing free sodium ions on the surface of the carbon nitride, performing suction filtration, and drying to obtain the sodium ion modified carbon nitride.
Example 3
10g of melamine was first weighed into an alumina crucible and calcined at 550 ℃ for 4h in an air atmosphere. And naturally cooling, taking out the sample, and grinding into powder to obtain the carbon nitride powder. Weighing 2g of carbon nitride powder and 10g of alkali metal chloride (5 g of sodium chloride and 5g of potassium chloride), uniformly grinding, calcining for 2h at 600 ℃ in a nitrogen atmosphere, carrying out ultrasonic dispersion on the obtained solid after natural cooling in water, removing free sodium and potassium ions on the surface of the carbon nitride, carrying out suction filtration, and drying to obtain the sodium and potassium ion modified carbon nitride.
Comparative example 1
10g of melamine was first weighed into an alumina crucible and calcined at 550 ℃ for 4h in an air atmosphere. And naturally cooling, taking out the sample, and grinding into powder to obtain the carbon nitride powder. Weighing 2g of carbon nitride powder and 286 mg of potassium chloride, adding into 10mL of water, stirring for 10 min, and then controlling the temperature at 80 ℃ to evaporate the water to dryness to obtain potassium ion loaded carbon nitride.
Fig. 1 is an X-ray powder diffraction pattern (XRD) of the ionothermal-synthesized potassium ion-modified carbon nitride and the immersion-synthesized potassium ion-supported carbon nitride obtained in example 1, and it can be seen that the degree of crystallinity of the carbon nitride is improved in the ionothermal-synthesized alkali metal ion-modified carbon nitride.
FIG. 2 is a Fourier transform infrared (FT-IR) spectrum of the ionothermal potassium ion-modified carbon nitride obtained in example 1 and the immersion potassium ion-supported carbon nitride, which is at 800 cm-1And 1200-1600 cm-1Interval corresponding to respiration vibration of oxazine ring and telescopic vibration of aromatic CN heterocyclic ring at 3200 cm-1The interval is mainly due to the existence of more non-bonded NH on the surface of the nano-layered carbon nitride2NH, it was confirmed that the product produced was a carbon nitride material.
FIG. 3 is a high resolution Transmission Electron Micrograph (TEM) and mapping image of the potassium ion modified carbon nitride obtained in example 1, from which a significant lattice fringe can be seen with a lattice fringe spacing of 0.31 nm. From mapping graph, it can be seen that the potassium ions are uniformly distributed.
Fig. 4 is an activity diagram of the potassium ion modified carbon nitride synthesized in example 1 for catalyzing COS hydrolysis, and from the diagram, we can obtain that the potassium ion loaded carbon nitride synthesized by the impregnation method has substantially no activity for catalyzing COS hydrolysis, while the potassium ion modified carbon nitride synthesized by the ionothermal method has high catalytic activity for COS hydrolysis, and in 10 hours of catalytic reaction, the COS conversion rate reaches 92%, and the activity does not change significantly, and the stability is good.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. The application of an alkali metal ion modified carbon nitride catalyst in carbonyl sulfide COS hydrolysis is characterized in that the modified alkali metal ion comprises Na+、K+And Cs+One or a combination of more of the above, wherein the content of alkali metal ions is 0.1-10 wt%, and the alkali metal ions in the catalyst are adsorbed on the amino nitrogen deprotonated by the carbon nitride through electrostatic interaction; the method for preparing the alkali metal ion modified carbon nitride catalyst comprises the following steps: (1) calcining the nitrogenous organic compound at the temperature of 450-650 ℃ for 2-4h in air or inert atmosphere to obtainTo carbon nitride;
(2) grinding and uniformly mixing the carbon nitride obtained in the step (1) and alkali metal halide;
(3) calcining the mixture obtained in the step (2) at the temperature of 650 ℃ in an inert atmosphere of 550-4 h to generate the carbon nitride modified by the alkali metal ions;
(4) and (4) mixing the solid powder obtained in the step (3) with deionized water, filtering to remove free alkali metal ions on the carbon nitride, and drying the obtained solid to obtain the alkali metal ion modified carbon nitride catalyst.
2. The use according to claim 1, wherein the nitrogen-containing organic compound in step (1) is one or more of cyanamide, dicyandiamide, melamine, ammonium thiocyanate, thiourea, guanidine carbonate and urea.
3. The use according to claim 1, wherein the alkali metal halide in step (2) is one or more of sodium chloride, potassium chloride, cesium chloride, sodium bromide, potassium bromide and cesium bromide; the mass ratio of the carbon nitride to the alkali metal halide is as follows: 1, (0.5-50).
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| CN110550612A (en) * | 2019-09-29 | 2019-12-10 | 福州大学 | Porous graphite phase carbon nitride nanosheet and preparation method and application thereof |
| CN113303491B (en) * | 2020-02-26 | 2022-11-11 | 湖南中烟工业有限责任公司 | Cigarette combustion cone structure regulator and preparation method and application thereof |
| CN111330620A (en) * | 2020-03-11 | 2020-06-26 | 中国科学技术大学 | Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof |
| CN112076776B (en) * | 2020-09-22 | 2021-08-31 | 福州大学 | Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof |
| CN114984992B (en) * | 2022-05-24 | 2023-09-05 | 中国科学院半导体研究所 | Preparation method and application of cesium-doped carbon nitride photocatalyst |
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