CN109985654A - A kind of carbon nitride catalyst and its preparation method and application of alkali metal ion modification - Google Patents
A kind of carbon nitride catalyst and its preparation method and application of alkali metal ion modification Download PDFInfo
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- CN109985654A CN109985654A CN201910341462.2A CN201910341462A CN109985654A CN 109985654 A CN109985654 A CN 109985654A CN 201910341462 A CN201910341462 A CN 201910341462A CN 109985654 A CN109985654 A CN 109985654A
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- alkali metal
- metal ion
- carbonitride
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- 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
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
Abstract
The invention belongs to catalyst technical fields, and in particular to a kind of carbon nitride catalyst, preparation method and the application of alkali metal ion modification.The catalyst, based on carbonitride, the alkali metal ion of the modification includes Na+、K+And Cs+One such or several combination, wherein 0.1~10wt% of content of alkali metal ion；Alkali metal ion in the catalyst is adsorbed on the ammonia nitrogen of carbonitride deprotonation by electrostatic interaction.Catalyst of the invention can be used as organic sulfur hydrolyst, show good catalytic activity and stability.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of carbon nitride catalyst of alkali metal ion modification, its
Preparation method and application.
Background technique
Carbonyl sulfur (COS) is primarily present form as a kind of organic sulfur, is widely present in the change such as coal, natural gas and petroleum
In stone raw material.Micro COS is easy to cause catalyst poisoning inactivation, production equipment and instrument in production process in industrial production
Corrode and influences quality of chemical products；In addition, not processed COS is discharged into atmosphere, can act on forming SO with oxygen2, promote
Photochemical reaction brings serious pollution environment, generates threat to human health.The physicochemical properties of carbonyl sulfur are stablized, and are in
Faintly acid, with H2S is compared, and has both been not easy to dissociate or has been not easy to liquefy, and removing H is generally used for2The method of S cannot be fully effective directly de-
Except COS.Currently, the main removing sulfuldioxide of COS has Hydrolyze method, reduction method, absorption process, absorption method, photodissociation method and oxidizing process etc.,
It is middle to be proved to be one of most efficient method using Hydrolyze method to remove COS, the basic principle is that: COS is under the action of catalyst
H is converted into water reaction2Then S removes H by other methods again2S, whole process is easy to operate, and energy charge is lower.Hydrolysis
The key technology of method is to develop the catalyst of high-efficiency and economic.
Current COS hydrolyst selects metal oxide or active carbon as carrier mostly, and further in the gold
Belong to and being prepared after load active component on oxide or active carbon.The COS hydrolyst of this kind of support type largely contains
Transition metal, it is expensive, and there are preparation processes that complicated, active component is easy falls off from carrier, activity stability difference etc.
Disadvantage.Therefore, by the innovation to COS hydrolyst, one kind is invented without transition metal and active component and carrier has
The COS hydrolyst of strong interaction has novelty.
In recent years, the carbonitride with graphite-like structure that element forms is enriched by carbon and nitrogen and receives extensive concern.Nitridation
Carbon polymer has good heat-resisting resistant to chemical etching, nontoxic and cheap, good biocompatibility and semiconductor property,
There is extraordinary application prospect in the energy and catalytic field at present.Nitrogenizing carbon surface has unpolymerized complete amino abundant
Group can be used as a kind of ideal base catalyst and supported catalyst agent carrier.COS hydrolysis is base catalyzed reactions, and is adopted
The carbonitride of the alkali metal ion modification synthesized with ionothermal synthesis has strong basicity and alkali metal ion can be mutual by electrostatic
Effect is adsorbed on not easily to fall off, good dispersion on nitridation carbon carrier.Therefore, the carbonitride of alkali metal ion modification is expected to become one
The effective catalyst of class COS hydrolysis.
Wait quietly disclosing a kind of graphite phase carbon nitride of alkali-metal-doped in visible light photocatalysis in " catalysis journal " in river
Comparative studies in hydrogen manufacturing, uses alkali metal hydroxide to be doped carbonitride, but since alkali metal hydroxide has
There is strong basicity, so that carbonitride main structure is subject to during the high temperature treatment process for graphite phase carbon nitride and alkali metal hydroxide
It destroys, the crystallinity of graphite phase carbon nitride is caused to decline.Therefore, л conjugated system declines, and alkalinity is not high.And the present invention use from
In the carbonitride of sub- thermal method synthetic alkali metal ion modification, using neutral alkali halide as ion solvent and carbonitride
It is reacted in high temperature, greatly improves the crystallinity of carbonitride, extend л conjugated system.Therefore, synthesized alkali metal from
The carbonitride of son modification has strong basicity.
Summary of the invention
In order to solve at least one aspect of the above-mentioned problems in the prior art and defect, the present invention provides one kind
The carbonitride hydrolytic catalyst of carbonyl sulfur and preparation method thereof of alkali metal ion modification.
To achieve the above object, the present invention adopts the following technical scheme:
First aspect present invention discloses a kind of carbon nitride catalyst of alkali metal ion modification, and the alkali metal ion includes Na+、K+And Cs+One or more of, wherein 0 .1 of content~10wt% of alkali metal ion.Alkali metal in the catalyst
Ion is adsorbed on the ammonia nitrogen of carbonitride deprotonation by electrostatic interaction.
Second aspect of the present invention discloses the carbon nitride catalyst preparation method of the alkali metal ion modification, including with
Lower step:
(1) organic compounds containing nitrogen is obtained into carbonitride under air or nitrogen atmosphere, 450-650 DEG C of calcining 2-4h；
(2) carbonitride and alkali metal chloride ground and mixed obtained step (1) is uniform；
(3) mixture for obtaining step (2) generates alkali metal ion modification in 550-650 DEG C of calcining 2-4h of inert atmosphere
Carbonitride；
(4) solid powder that step (3) obtains is mixed with deionized water, is then filtered, removed unadsorbed on carbonitride
Alkali metal ion, the carbon nitride catalyst that the dry at least 6h of obtained solid is modified to get the alkali metal ion.
Organic compounds containing nitrogen described in above-mentioned steps (1) is cyanamide, dicyandiamide, melamine, thiocyanic acid amine, sulphur
One or more of urea, guanidine carbonate and urea.
Above-mentioned steps (2) alkali halide is sodium chloride, potassium chloride, cesium chloride, sodium bromide, potassium bromide and bromination
One or more of caesium.The mass ratio of carbonitride and alkali halide are as follows: 1:(0.5~50).
Third aspect present invention discloses the carbon nitride catalyst of the alkali metal ion modification for catalyzing hydrolysis COS
Purposes.
Remarkable advantage of the invention is:
(1) synthetic method safety and environmental protection of the present invention, preparation process is simple, and mild condition is controllable.
(2) without transition metal in the carbon nitride catalyst for the alkali metal ion modification that the present invention synthesizes, raw material is cheap；Alkali
Metal ion is dispersed on carbonitride, and has strong interaction with carbonitride, not easily to fall off.
(3) carbon nitride catalyst for the alkali metal ion modification that the present invention synthesizes, can be used for catalyzing hydrolysis COS reaction,
Catalysis in 10 hours is reacted in (70 DEG C) tests, and COS conversion ratio reaches 92%, and significant change does not occur for activity, and stability is good.
Detailed description of the invention
Fig. 1 is that the resulting ionothermal synthesis of embodiment 1 synthesizes the carbonitride of potassium ion modification and infusion process synthesizes potassium ion and bears
The X-ray powder diffraction figure (XRD) of the carbonitride of load;
Fig. 2 is that the resulting ionothermal synthesis of embodiment 1 synthesizes the carbonitride of potassium ion modification and infusion process synthesizes potassium ion load
Infrared (FTIR) spectrogram of carbonitride；
Fig. 3 is the carbonitride transmission electron microscope picture (TEM) and mapping figure of the modification of potassium ion synthesized by embodiment 1；
Fig. 4 is the carbonitride of the modification of potassium ion synthesized by embodiment 1 and infusion process synthesizes the carbonitride catalysis that potassium ion loads
The activity figure of (70 DEG C) COS hydrolysis.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
10g melamine is weighed first to be put in alumina crucible, calcines 4h under the conditions of 550 DEG C in air atmosphere.Naturally cold
But sample is taken out afterwards to be ground into powder, and obtains nitridation carbon dust.Weigh 2g nitridation carbon dust and 10g alkali metal chloride (chlorine
Change potassium) grinding uniformly, calcine 2h at 600 DEG C in nitrogen atmosphere, the solid obtained after natural cooling ultrasonic disperse in water removes
The potassium ion to dissociate on nitridation carbon surface is removed, is dried after suction filtration, obtains the carbonitride of potassium ion modification.
Embodiment 2
10g melamine is weighed first to be put in alumina crucible, calcines 2h under the conditions of 550 DEG C in air atmosphere.Naturally cold
But sample is taken out afterwards to be ground into powder, and obtains nitridation carbon dust.Weigh 2g nitridation carbon dust and 10g alkali metal chloride (chlorine
Change sodium) grinding uniformly, calcine 2h at 600 DEG C in nitrogen atmosphere, the solid obtained after natural cooling ultrasonic disperse in water removes
The sodium ion to dissociate on nitridation carbon surface is removed, is dried after suction filtration, obtains the carbonitride of sodium ion modification.
Embodiment 3
10g melamine is weighed first to be put in alumina crucible, calcines 4h under the conditions of 550 DEG C in air atmosphere.Naturally cold
But sample is taken out afterwards to be ground into powder, and obtains nitridation carbon dust.Weigh 2g nitridation carbon dust and 10g alkali metal chloride (5g
Sodium chloride and 5g potassium chloride) it grinds uniformly, 2h is calcined at 600 DEG C in nitrogen atmosphere, the solid obtained after natural cooling is in water
Middle ultrasonic disperse removes carbonitride upstream surface from sodium and potassium ion, dries after suction filtration, obtains the nitridation of sodium and potassium ion modification
Carbon.
Comparative example 1
10g melamine is weighed first to be put in alumina crucible, calcines 4h under the conditions of 550 DEG C in air atmosphere.Naturally cold
But sample is taken out afterwards to be ground into powder, and obtains nitridation carbon dust.2g nitridation carbon dust is weighed to be added to 286 mg potassium chloride
In 10mL water, 10 min are stirred, then temperature is controlled, water is evaporated at 80 DEG C, obtain the carbonitride of potassium ion load.
Fig. 1 is that the resulting ionothermal synthesis of embodiment 1 synthesizes the carbonitride of potassium ion modification and infusion process synthesizes potassium ion and bears
The X-ray powder diffraction figure (XRD) of the carbonitride of load, as can be seen from the figure ionothermal synthesis synthetic alkali metal ion modification
The crystallinity of carbonitride is improved in carbonitride.
Fig. 2 is that the resulting ionothermal synthesis of embodiment 1 synthesizes the carbonitride of potassium ion modification and infusion process synthesizes potassium ion and bears
The Fourier transform infrared spectroscopy figure (FT-IR) of the carbonitride of load, as can be seen from the figure in 800 cm-1With 1200 ~ 1600
cm-1Section, they correspond respectively to the breathing vibration and armaticity CN heterocycle stretching vibration of piperazine ring, in 3200 cm-1Section master
Carbon surface is nitrogenized due to nano lamellar there are relatively more NH not being bonded2, caused by NH, it was demonstrated that the product of preparation is nitridation
Carbon material.
Fig. 3 is the high-resolution-ration transmission electric-lens figure (TEM) and mapping of the carbonitride of the resulting potassium ion of embodiment 1 modification
Figure, apparent lattice fringe, lattice fringe spacing are 0 .31nm as we can see from the figure.It can be seen that potassium from mapping figure
Ion distribution is uniform.
Fig. 4 be embodiment 1 synthesized by potassium ion modification carbonitride be catalyzed COS hydrolysis activity figure, from figure we
It can be concluded that not having to be catalyzed the activity of COS hydrolysis substantially using the carbonitride of the potassium ion load of infusion process synthesis, and use ion
The carbonitride of the potassium ion modification of thermal method synthesis COS hydrolyzation catalysis activity with higher, in catalysis reaction in 10 hours,
COS conversion ratio reaches 92%, and significant change does not occur for activity, and stability is good.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of carbon nitride catalyst of alkali metal ion modification, which is characterized in that the alkali metal ion of the modification includes Na+、
K+And Cs+One such or several combination, wherein the content of alkali metal ion is 0 .1~10wt%.
2. the carbon nitride catalyst of alkali metal ion modification according to claim 1, which is characterized in that the base catalyst
In alkali metal ion be adsorbed on by electrostatic interaction on the ammonia nitrogen of carbonitride deprotonation.
3. a kind of method for the carbonitride base catalyst for preparing alkali metal ion modification as described in claim 1, feature exist
In, comprising the following steps: (1) organic compounds containing nitrogen is obtained under air or inert atmosphere, 450-650 DEG C of calcining 2-4h
Carbonitride；
(2) carbonitride and alkali halide ground and mixed obtained step (1) is uniform；
(3) mixture for obtaining step (2) generates alkali metal ion modification in 550-650 DEG C of calcining 2-4h of inert atmosphere
Carbonitride；
(4) solid powder that step (3) obtains is mixed with deionized water, is then filtered, remove the free alkali on carbonitride
Metal ion, by the dry carbonitride base catalyst modified to get the alkali metal ion of obtained solid.
4. preparation method according to claim 3, which is characterized in that organic compounds containing nitrogen described in step (1) is cyanogen
One or more of amine, dicyandiamide, melamine, thiocyanic acid amine, thiocarbamide, guanidine carbonate and urea.
5. preparation method according to claim 3, which is characterized in that step (2) alkali halide be sodium chloride,
One or more of potassium chloride, cesium chloride, sodium bromide, potassium bromide and cesium bromide；The quality of carbonitride and alkali halide
Than are as follows: 1:(0.5~50).
6. a kind of carbon nitride catalyst of alkali metal ion modification according to claim 1 is in carbonyl sulfur COS hydrolysis
Using.
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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 |
| 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 |
| CN112076776A (en) * | 2020-09-22 | 2020-12-15 | 福州大学 | Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof |
| CN113303491A (en) * | 2020-02-26 | 2021-08-27 | 湖南中烟工业有限责任公司 | Cigarette combustion cone structure regulator and preparation method and application thereof |
| CN114984992A (en) * | 2022-05-24 | 2022-09-02 | 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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| 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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