CN114790001B - Polyacid functionalized nitrogen-rich porous carbon and preparation method and application thereof - Google Patents
Polyacid functionalized nitrogen-rich porous carbon and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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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
- B01D53/81—Solid phase processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/20—Regeneration or reactivation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
Abstract
The invention belongs to the technical field of air pollution control, and particularly relates to polyacid functionalized nitrogen-rich porous carbon, and a preparation method and application thereof. The invention mixes polyacid compound, water and macrocyclic compound to carry on the ultrasound, get clathrate compound; the polyacid compound comprises one or more of polyoxometalate and polyoxometalate monomers; and mixing the inclusion compound, the nitrogen-containing compound, the activating agent and the carbon source for carbonization reaction to obtain the polyacid functionalized nitrogen-rich porous carbon. The preparation method provided by the invention has the advantages of simple steps, convenient operation, high product yield, low cost and good economic and social benefits. The polyacid functionalized nitrogen-rich porous carbon prepared by the method is not only suitable for medium and low temperature conditions, but also has high mass transfer characteristics, and can realize high-efficiency removal of hydrogen sulfide.
Description
Technical Field
The invention belongs to the technical field of air pollution control, and particularly relates to polyacid functionalized nitrogen-rich porous carbon, and a preparation method and application thereof.
Background
Hydrogen sulfide (H) 2 S) is a malodorous acid gas widely existing in various industrial gases (natural gas, biogas, etc.) and industrial activities (fuel hydrogenation, landfill, etc.), which is strongly corrosive and toxic, and can not only cause serious corrosion of industrial equipment and pipelines, increase operation and maintenance costs, but also pose a great threat to the life health of related practitioners. In addition, hydrogen sulfide is converted to two by combustion reactionSulfur oxides, in turn, can lead to acid rain, which is one of the causes of atmospheric pollution. Therefore, the efficient removal and conversion of hydrogen sulfide is a key ring for industrial safety production.
The current desulfurization processes are classified into dry and wet processes. The dry desulfurization is mainly carried out by utilizing porous materials such as carbon materials, molecular sieves, metal oxides and the like through adsorption or catalytic oxidation. The dry desulfurization has the advantages of high sensitivity, basically no corrosion, wide applicable conditions, simple operation, low running cost and the like, but due to the existence of CO in industrial gas 2 Acid gases such as common physical adsorption or acid-base reaction are not easy to realize high-efficiency removal of hydrogen sulfide. Compared with the traditional carbon, the nitrogen-rich porous carbon (NPC) not only has the structural properties of large specific surface area, rich pore structure and the like, but also has the chemical characteristics of enhanced alkaline site, surface polarity, catalytic activity and the like, but the NPC catalyst needs to be used under the condition of higher temperature when the temperature is higher than that of the NPC catalyst>NPC can maintain stable desulfurization ability at 180 ℃, but at temperature<At 180 ℃, the action of sulfur deposition can lead to the loss of the catalytic activity of NPC, thereby affecting the desulfurization capability of NPC.
Disclosure of Invention
The invention aims to provide polyacid functionalized nitrogen-rich porous carbon, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of polyacid functionalized nitrogen-rich porous carbon comprises the following steps:
(1) Mixing polyacid compounds, water and macrocyclic compounds for ultrasound to obtain inclusion compounds; the polyacid compound comprises one or more of polyoxometalate and polyoxometalate monomers;
(2) And mixing the inclusion compound, the nitrogen-containing compound, the activating agent and the carbon source for carbonization reaction to obtain the polyacid functionalized nitrogen-rich porous carbon.
Preferably, the mass ratio of the polyacid compound to the macrocyclic compound is 1:0.0005 to 2000; the mass ratio of the polyacid compound to the water is 1: 0.0001-300; the mass ratio of the inclusion compound to the nitrogen-containing compound is 1:0.0025 to 300; the mass ratio of the inclusion compound to the activator is 1:0.0025 to 300; the mass ratio of the inclusion compound to the carbon source is 1:0.0025 to 300.
Preferably, the temperature of the carbonization reaction is 300-1000 ℃ and the time is 0.5-10 h.
Preferably, the macrocyclic compound comprises one or more of cyclodextrin, calixarene, crown ether, column arene and cucurbituril; the polyoxometalate comprises one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid; the polyoxometalate monomer comprises one or more of sodium tungstate, sodium molybdate and ammonium molybdate.
Preferably, the nitrogen-containing compound comprises one or more of an organic nitrogen-containing compound and an inorganic nitrogen-containing compound; the activator comprises one or more of alkali metal bicarbonate and alkali metal hydroxide; the carbon source is an organic carbon source.
The invention also provides the polyacid functionalized nitrogen-rich porous carbon prepared by the preparation method.
Preferably, the nitrogen content of the nitrogen-rich porous carbon in the polyacid functionalized nitrogen-rich porous carbon is 0.5% -10%; the specific surface area of the nitrogen-rich porous carbon is 100-2000 m 2 /g; the aperture of the nitrogen-rich porous carbon is 1-50 nm.
The invention also provides application of the polyacid functionalized nitrogen-rich porous carbon or the polyacid functionalized nitrogen-rich porous carbon obtained by the preparation method in removal and conversion of hydrogen sulfide.
Preferably, the application comprises the steps of: and filling the polyacid functionalized nitrogen-rich porous carbon into a quartz tube, constructing a fixed bed reactor, introducing mixed gas to be treated, and removing hydrogen sulfide and converting into elemental sulfur.
Preferably, the airspeed of the gas mixture is 3000 to 50000 mL/(g.h).
The invention provides a preparation method of polyacid functionalized nitrogen-rich porous carbon, which comprises the following steps: mixing polyacid compounds, water and macrocyclic compounds for ultrasound to obtain inclusion compounds; and mixing the inclusion compound, the nitrogen-containing compound, the activating agent and the carbon source for carbonization reaction to obtain the polyacid functionalized nitrogen-rich porous carbon. The preparation method provided by the invention has the advantages of simple steps, convenient operation, high product yield, low cost and good economic and social benefits.
The invention also provides the polyacid functionalized nitrogen-rich porous carbon prepared by the preparation method. The polyacid functionalized nitrogen-rich porous carbon prepared by the method comprises nitrogen-rich porous carbon and inclusion compound loaded on the surface of the nitrogen-rich porous carbon. The polyacid functionalized nitrogen-rich porous carbon provided by the invention is based on the rich pore structure of the nitrogen-rich porous carbon, when the polyacid functionalized nitrogen-rich porous carbon is used as a desulfurizing agent, hydrogen sulfide is captured through surface pores, and then high-valence metal sites with high redox performance, active sites such as pyridine nitrogen and the like provided by the nitrogen-rich porous carbon are provided through polyacid compounds, so that the hydrogen sulfide is selectively removed and converted into a sulfur simple substance. The method organically combines the high redox performance of polyacid compounds with the high selective desulfurization of nitrogen-rich porous carbon, utilizes the synergistic effect between the polyacid compounds and the nitrogen-rich porous carbon to establish a solid-phase desulfurization system with the characteristics of high removal and high conversion of wet process and high precision of dry process, converts hydrogen sulfide into available elemental sulfur, and realizes the recycling conversion of the hydrogen sulfide.
In addition, the multi-acid functional nitrogen-rich porous carbon provided by the invention utilizes the characteristic of a special three-dimensional cavity structure of a macrocyclic compound, is used as a main molecule and a pore-forming agent for inclusion of the multi-acid compound, forms an inclusion compound, and utilizes the finite field effect of the macrocyclic compound on the multi-acid compound to regulate and control preparation of the mono-disperse multi-acid site modified nitrogen-rich biochar, so that the accumulation of the multi-acid compound is reduced, the multi-acid compound is more uniformly dispersed, the utilization rate of the multi-acid compound is improved, and the problem that a multi-acid compound liquid-phase desulfurization system is not easy to recover is solved; and the desulfurization durability of the material in the low-temperature stage is increased by the pore-forming effect of the macrocyclic compound, so that the hydrogen sulfide is efficiently and selectively removed under the medium-low-temperature normal-pressure condition. In addition, the polyacid functionalized nitrogen-rich porous carbon provided by the invention has the characteristics of high removal rate and environmental protection, can maintain stable desulfurization rate in the environment with low temperature and interference gas, and is suitable for the requirements of complex working condition application.
Furthermore, the invention adopts the agricultural waste biomass as a carbon source, so that the hydrogen sulfide is efficiently removed and converted into elemental sulfur, the recycling of sulfur resources is realized, and the purpose of high-value utilization of the agricultural waste is achieved.
The invention also provides application of the polyacid functionalized nitrogen-rich porous carbon in hydrogen sulfide removal and conversion. The polyacid functionalized nitrogen-rich porous carbon is applied to hydrogen sulfide removal and conversion, so that the high-efficiency selective removal and resource conversion of hydrogen sulfide under the conditions of low temperature and normal pressure can be realized, and the polyacid functionalized nitrogen-rich porous carbon has the advantages of low energy consumption, no corrosion and no pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing changes in hydrogen sulfide removal rates at room temperature of the polyacid-functionalized nitrogen-rich porous carbon prepared in example 1, the nitrogen-rich porous carbon prepared in comparative example 1, and the polyacid-nitrogen-rich porous carbon prepared in comparative example 2.
Fig. 2 is SEM images (a and b) of the nitrogen-enriched porous carbon prepared in comparative example 1 and SEM images (c and d) of the polyacid-functionalized nitrogen-enriched porous carbon prepared in example 1.
Fig. 3 is a TEM image (a) of the nitrogen-enriched porous carbon prepared in comparative example 1 and a TEM (b) of the polyacid-functionalized nitrogen-enriched porous carbon prepared in example 1.
FIG. 4 is an XRD comparison of elemental sulfur (Product S) and elemental sulfur recovered in example 1.
FIG. 5 is a graph showing the change in hydrogen sulfide removal rate at 100℃of the polyacid-functionalized nitrogen-rich porous carbon prepared in example 3.
FIG. 6 is a graph showing the change in hydrogen sulfide removal rate at 200℃for the polyacid functionalized nitrogen-rich porous carbon prepared in example 4.
Detailed Description
The invention provides a preparation method of polyacid functionalized nitrogen-rich porous carbon, which comprises the following steps:
(1) Mixing polyacid compounds, water and macrocyclic compounds for ultrasound to obtain inclusion compounds;
(2) And mixing the inclusion compound, the nitrogen-containing compound, the activating agent and the carbon source for carbonization reaction to obtain the polyacid functionalized nitrogen-rich porous carbon.
The invention mixes polyacid compound, water and macrocyclic compound to carry on the ultrasound, get clathrate compound. In the present invention, the polyoxometalate preferably includes one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid; the polyoxometalate monomer preferably comprises one or more of sodium tungstate, sodium molybdate and ammonium molybdate; the macrocyclic compound preferably comprises one or more of cyclodextrin, calixarene, crown ether, column arene and cucurbituril; the cyclodextrin is preferably beta-cyclodextrin; the calixarene is preferably calix [4] arene; the crown ether is preferably 18 crown ether 6; the column arene is preferably a column [6] arene; the cucurbituril is preferably cucurbituril [6] urils; the water is preferably deionized water and/or purified water; the mass ratio of the polyacid compound to the water is preferably 1:0.0001 to 300, more preferably 1:0.1 to 200, more preferably 1:1 to 100. In the present invention, the mixing preferably includes: dissolving polyacid compound in water, and adding macrocyclic compound. In the present invention, the time of the ultrasonic wave is preferably 5 to 420 minutes, more preferably 50 to 350 minutes, further preferably 150 to 250 minutes; the frequency of the ultrasonic wave is preferably 20 to 80KHz, more preferably 30 to 60KHz, and even more preferably 40 to 50KHz.
And after the inclusion compound is obtained, mixing the inclusion compound, the nitrogen-containing compound, the activating agent and the carbon source for carbonization reaction to obtain the polyacid functionalized nitrogen-rich porous carbon. In the present invention, the mass ratio of the clathrate and the nitrogen-containing compound is preferably 1:0.0025 to 300, more preferably 1:0.1 to 200, more preferably 1:1 to 100; the nitrogen-containing compound preferably includes one or more of an organic nitrogen-containing compound and an inorganic nitrogen-containing compound; the organic nitrogen-containing compound preferably comprises one or more of melamine, dicyandiamide, chitosan, ammonium oxalate and urea.
In the invention, the mass ratio of the inclusion compound to the activator is preferably 1:0.0025 to 300, more preferably 1:0.1 to 200, more preferably 1:1 to 100; the activator preferably comprises one or more of an alkali metal bicarbonate and an alkali metal hydroxide; the alkali metal bicarbonate preferably comprises one or more of sodium bicarbonate and potassium bicarbonate; the alkali metal hydroxide preferably includes one or more of sodium hydroxide and potassium hydroxide.
In the present invention, the mass ratio of the clathrate and the carbon source is preferably 1:0.0025 to 300, more preferably 1:0.1 to 240, more preferably 1:1 to 180; the carbon source is preferably an organic carbon source; the organic carbon source is preferably agricultural waste biomass; the agricultural waste biomass preferably comprises one or more of corn stalks, peanut hulls, rice hulls, wheat straw and soybean straw.
In the present invention, the temperature of the carbonization reaction is preferably 300 to 1200 ℃, more preferably 400 to 900 ℃, still more preferably 500 to 800 ℃, and the time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, still more preferably 1 to 5 hours; the carbonization reaction is preferably carried out under an inert atmosphere; the inert atmosphere is preferably nitrogen; the flow rate of the nitrogen gas is preferably 10-400 mL/min, more preferably 30-300 mL/min, and even more preferably 50-200 mL/min; the apparatus for the carbonization reaction is preferably a tube furnace.
The invention also provides the polyacid functionalized nitrogen-rich porous carbon prepared by the preparation method.
In the invention, the nitrogen content of the nitrogen-rich porous carbon in the polyacid functionalized nitrogen-rich porous carbon is preferably 0.5-10%, more preferably 1-8%, and even more preferably 3-6%; the specific surface area of the nitrogen-rich porous carbon is preferably 100-2000 m 2 Preferably 300 to 1500m 2 Preferably 500 to 1000m 2 /g; the enrichment ofThe pore diameter of the nitrogen porous carbon is preferably 1 to 50nm, more preferably 3 to 15nm, and still more preferably 8 to 12nm.
The invention also provides the polyacid functionalized nitrogen-rich porous carbon obtained by the preparation method of the scheme or the application of the polyacid functionalized nitrogen-rich porous carbon in hydrogen sulfide removal and conversion.
In the present invention, the application preferably includes the steps of: and filling the polyacid functionalized nitrogen-rich porous carbon into a quartz tube, constructing a fixed bed reactor, introducing mixed gas to be treated, and removing hydrogen sulfide and converting into elemental sulfur.
In the present invention, the inner diameter of the quartz tube is preferably 8mm, and the length is preferably 40cm; the components of the gas mixture preferably include hydrogen sulfide, oxygen and a carrier gas; the carrier gas is preferably nitrogen; the concentration of hydrogen sulfide in the mixed gas is preferably 500-2000 mg/m 3 More preferably 800 to 1500mg/m 3 Further preferably 1000 to 1200mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The space velocity of the gas mixture is preferably 3000 to 50000 mL/(g.h), more preferably 10000 to 30000 mL/(g.h); the desulfurization is preferably carried out simultaneously with H 2 H of S gas analyzer to reactor outlet 2 S concentration is dynamically detected; the desulfurization is preferably carried out by adopting NaOH solution to carry out tail gas absorption treatment. In the invention, after the hydrogen sulfide is removed and converted into elemental sulfur, the elemental sulfur is recovered preferably by solvent extraction or purge condensation, and then the polyacid functionalized nitrogen-rich porous carbon is purged and regenerated by ozone. The solvent in the solvent extraction is preferably carbon disulphide; the purge condensation preferably employs hot nitrogen; the temperature of the purging regeneration is preferably from normal temperature to 200 ℃, more preferably from normal temperature to 100 ℃, and even more preferably from normal temperature; the time for the purge regeneration is preferably 10 to 360 minutes, more preferably 10 to 100 minutes. According to the method, sulfur simple substances and the like remained in the pore canal of the polyacid functional nitrogen-rich porous carbon are cleared through purging condensation or solvent extraction, so that the polyacid functional nitrogen-rich porous carbon is ensured to be fully contacted with the mixed gas, and the catalytic effect is ensured.
For further explanation of the present invention, the polyacid functionalized nitrogen-rich porous carbon provided by the present invention is described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 4g of phosphomolybdic acid, dissolving the phosphomolybdic acid in 20mL of purified water, weighing 5g of beta cyclodextrin, and performing ultrasonic treatment for 120min to obtain an inclusion compound;
weighing 0.5g of the inclusion compound, 4g of ammonium oxalate and 4g of sodium bicarbonate, mixing the inclusion compound, the 4g of ammonium oxalate and the 4g of sodium bicarbonate with 6g of rice hulls, transferring the mixture into a tube furnace, introducing nitrogen, controlling the flow rate of the nitrogen to be 60mL/min, performing carbonization reaction in a nitrogen atmosphere, controlling the reaction temperature to be 800 ℃, and reacting for 1h to obtain polyacid functionalized nitrogen-rich porous carbon;
filling 0.2g of the polyacid functionalized nitrogen-rich porous carbon into a quartz tube with the inner diameter of 8mm and the length of 40cm, and introducing mixed gas with the flow of 100mL/min under the room temperature condition for desulfurization, wherein the mixed gas comprises hydrogen sulfide, oxygen and nitrogen, and the concentration of the hydrogen sulfide is 1000mg/m 3 By H 2 S gas analyzer for tail gas H 2 S gas concentration is dynamically detected, and tail gas is absorbed by NaOH solution;
at 200 ℃, the desulfurized polyacid is functionalized into nitrogen-rich porous carbon, sulfur recovery is carried out through carbon disulfide extraction, and then ozone is utilized to purge for 60min for regeneration treatment.
Example 2
Weighing 4g of phosphomolybdic acid, dissolving the phosphomolybdic acid in 20mL of purified water, weighing 5g of beta-cyclodextrin, and performing ultrasonic treatment for 120min to obtain an inclusion compound;
weighing 0.25g of the inclusion compound, 4g of ammonium oxalate and 4g of sodium bicarbonate, mixing the inclusion compound, the 4g of ammonium oxalate and the 4g of sodium bicarbonate with 6g of rice hulls, transferring the mixture into a tube furnace, introducing nitrogen, controlling the flow rate of the nitrogen to be 60mL/min, performing carbonization reaction in a nitrogen atmosphere, controlling the reaction temperature to be 800 ℃, and reacting for 1h to obtain polyacid functionalized nitrogen-rich porous carbon;
filling 0.2g of the polyacid functionalized nitrogen-rich porous carbon into a quartz tube with the inner diameter of 8mm and the length of 40cm, and introducing mixed gas with the flow of 100mL/min under the room temperature condition for desulfurization, wherein the mixed gas comprises hydrogen sulfide, oxygen and nitrogen, and the sulfur is treated by the steps ofHydrogen concentration of 1000mg/m 3 By H 2 S gas analyzer for tail gas H 2 S gas concentration is dynamically detected, and tail gas is absorbed by NaOH solution;
and (3) at 200 ℃, performing sulfur recovery on the desulfurized polyacid functionalized nitrogen-rich porous carbon by blowing and condensing hot nitrogen, and then performing regeneration treatment by blowing and condensing ozone for 60 min.
Example 3
Weighing 4g of phosphomolybdic acid, dissolving the phosphomolybdic acid in 20mL of purified water, weighing 5g of beta cyclodextrin, and performing ultrasonic treatment for 120min to obtain an inclusion compound;
weighing 0.5g of the inclusion compound, 4g of ammonium oxalate and 4g of sodium bicarbonate, mixing the inclusion compound, the 4g of ammonium oxalate and the 4g of sodium bicarbonate with 6g of rice hulls, transferring the mixture into a tube furnace, introducing nitrogen, controlling the flow rate of the nitrogen to be 60mL/min, performing carbonization reaction in a nitrogen atmosphere, controlling the reaction temperature to be 800 ℃, and reacting for 1h to obtain polyacid functionalized nitrogen-rich porous carbon;
filling 0.2g of the polyacid functionalized nitrogen-rich porous carbon into a quartz tube with the inner diameter of 8mm and the length of 40cm, and introducing mixed gas with the flow of 100mL/min at the temperature of 100 ℃ for desulfurization, wherein the mixed gas comprises hydrogen sulfide, oxygen and nitrogen, and the concentration of the hydrogen sulfide is 1000mg/m 3 By H 2 S gas analyzer for tail gas H 2 S gas concentration is dynamically detected, and tail gas is absorbed by NaOH solution;
at 200 ℃, the desulfurized polyacid is functionalized into nitrogen-rich porous carbon, sulfur recovery is carried out through carbon disulfide extraction, and then ozone is utilized to purge for 60min for regeneration treatment.
Example 4
Weighing 4g of phosphomolybdic acid, dissolving the phosphomolybdic acid in 20mL of purified water, weighing 5g of beta cyclodextrin, and performing ultrasonic treatment for 120min to obtain an inclusion compound;
weighing 0.5g of the inclusion compound, 4g of ammonium oxalate and 4g of sodium bicarbonate, mixing the inclusion compound, the 4g of ammonium oxalate and the 4g of sodium bicarbonate with 6g of rice hulls, transferring the mixture into a tube furnace, introducing nitrogen, controlling the flow rate of the nitrogen to be 60mL/min, performing carbonization reaction in a nitrogen atmosphere, controlling the reaction temperature to be 800 ℃, and reacting for 1h to obtain polyacid functionalized nitrogen-rich porous carbon;
filling 0.2g of the polyacid functionalized nitrogen-rich porous carbon into a quartz tube with the inner diameter of 8mm and the length of 40cm, and introducing mixed gas with the flow rate of 100mL/min at the temperature of 200 ℃ for desulfurization, wherein the mixed gas comprises hydrogen sulfide, oxygen and nitrogen, and the concentration of the hydrogen sulfide is 1000mg/m 3 By H 2 S gas analyzer for tail gas H 2 S gas concentration is dynamically detected, and tail gas is absorbed by NaOH solution.
Comparative example 1
Weighing 4g of ammonium oxalate and 4g of sodium bicarbonate, mixing the ammonium oxalate and the 4g of sodium bicarbonate with 6g of rice hulls, transferring the mixture into a tube furnace, introducing nitrogen, controlling the flow of the nitrogen to be 60mL/min, performing carbonization reaction in a nitrogen atmosphere, controlling the reaction temperature to be 800 ℃, and reacting for 1h to obtain nitrogen-rich porous carbon;
filling 0.2g of the nitrogen-rich porous carbon into a quartz tube with the inner diameter of 8mm and the length of 40cm, and introducing a mixed gas with the flow rate of 100mL/min under the condition of room temperature for desulfurization, wherein the mixed gas comprises hydrogen sulfide, oxygen and nitrogen, and the concentration of the hydrogen sulfide is 1000mg/m 3 By H 2 S gas analyzer for tail gas H 2 S gas concentration is dynamically detected, and tail gas is absorbed by NaOH solution.
Comparative example 2
Weighing 0.15g of phosphomolybdic acid, 4g of ammonium oxalate and 4g of sodium bicarbonate, mixing the phosphomolybdic acid, 4g of ammonium oxalate and 4g of sodium bicarbonate with 6g of rice hulls, transferring the mixture into a tube furnace, introducing nitrogen, controlling the flow rate of the nitrogen to be 60mL/min, performing carbonization reaction in a nitrogen atmosphere, controlling the reaction temperature to be 800 ℃, and reacting for 1h to obtain a polyacid compound, namely nitrogen-rich porous carbon;
filling 0.2g of polyacid compound-nitrogen-rich porous carbon into a quartz tube with an inner diameter of 8mm and a length of 40cm, and introducing a mixed gas with a flow rate of 100mL/min under the condition of room temperature to desulfurize, wherein the mixed gas comprises hydrogen sulfide, oxygen and nitrogen, and the concentration of the hydrogen sulfide is 1000mg/m 3 By H 2 S gas analyzer for tail gas H 2 S gas concentration is dynamically detected, and tail gas is absorbed by NaOH solution.
By H 2 S gas analyzer exhaust gas H of example 1 and comparative examples 1 to 2 2 The S gas concentration was dynamically measured, and the results are shown in FIG. 1.
As can be seen from fig. 1, the removal efficiency of the nitrogen-rich porous carbon prepared in comparative example 1 has been started to decrease at 30min and has been rapidly decreased to 40% or less at 60min, the removal efficiency of the polyacid-nitrogen-rich porous carbon prepared in comparative example 2 was started to decrease at 40min and has been rapidly decreased to about 50% at 60min, and the removal efficiency of the polyacid-functionalized nitrogen-rich porous carbon prepared in example 1 of the present invention was decreased at 60 min. In addition, the removal efficiency of the polyacid functionalized nitrogen-rich porous carbon prepared in the embodiment 1 of the invention is still maintained above 70% in 80min, which is more than 2 times of that of the comparative examples 1 and 2. In addition, at 120min, the removal efficiency of comparative examples 1 and 2 was about 20%, while the removal efficiency of the polyacid-functionalized nitrogen-rich porous carbon provided by the invention was about 35%, which is still much higher than that of comparative examples 1 and 2. Therefore, the polyacid functionalized nitrogen-rich porous carbon provided by the invention can well keep activity under the medium-low temperature condition.
The scanning electron microscope detection is carried out on the polyacid functionalized nitrogen-rich porous carbon prepared in the embodiment 1 and the nitrogen-rich porous carbon prepared in the comparative example 1, and the result is shown in fig. 2, wherein a is a cross-sectional scanning electron microscope image of the nitrogen-rich porous carbon prepared in the comparative example 1 when the scale is 2 μm, b is a cross-sectional scanning electron microscope image of the nitrogen-rich porous carbon prepared in the comparative example 1 when the scale is 500nm, c is a cross-sectional scanning electron microscope image of the polyacid functionalized nitrogen-rich porous carbon prepared in the embodiment 1 when the scale is 2 μm, and d is a cross-sectional scanning electron microscope image of the polyacid functionalized nitrogen-rich porous carbon prepared in the embodiment 1 when the scale is 500 nm. As can be seen from fig. 2, the polyacid-functionalized nitrogen-rich porous carbon prepared in example 1 of the present invention has a porous structure that is rich in porosity, compared to the nitrogen-rich porous carbon prepared in comparative example 1.
The polyacid functionalized nitrogen-rich porous carbon prepared in example 1 and the nitrogen-rich porous carbon prepared in comparative example 1 were subjected to transmission electron microscopy, a is a transmission electron microscopy image of the nitrogen-rich porous carbon prepared in comparative example 1 when the scale is 100nm, and b is a transmission electron microscopy image of the polyacid functionalized nitrogen-rich porous carbon prepared in example 1 of the invention when the scale is 100 nm. As can be seen from fig. 3, compared with the nitrogen-enriched porous carbon prepared in comparative example 1, the clathrate compound in the polyacid-functionalized nitrogen-enriched porous carbon prepared in example 1 of the present invention is uniformly distributed, and agglomeration of polyacid compounds is avoided.
The elemental sulfur recovered in example 1 of the present invention was subjected to X-ray diffraction analysis, and the upper image, product S, is an X-ray diffraction pattern of elemental sulfur recovered in example 1 of the present invention, and the lower image is an X-ray diffraction pattern of elemental sulfur. According to the results of fig. 4, the XRD patterns of the elemental sulfur and elemental sulfur recovered in example 1 of the present invention are highly consistent, and it can be seen that the polyacid functionalized nitrogen-rich porous carbon provided by the present invention can successfully convert hydrogen sulfide into elemental sulfur, thereby realizing the recycling conversion of sulfur.
By H 2 S gas analyzer for tail gas H of example 3 and example 4 2 The S gas concentration was dynamically detected, and the results are shown in FIG. 5 and FIG. 6. Wherein, fig. 5 is a graph showing the change of the hydrogen sulfide removal rate of the polyacid functionalized nitrogen-rich porous carbon prepared in example 3 at 100 ℃, and fig. 6 is a graph showing the change of the hydrogen sulfide removal rate of the polyacid functionalized nitrogen-rich porous carbon prepared in example 4 at 200 ℃.
According to fig. 5, the removal rate of the polyacid functionalized nitrogen-rich porous carbon prepared in example 3 is maintained at 100% within 80min and can be maintained at more than 50% within 250min at 100 ℃, so that the polyacid functionalized nitrogen-rich porous carbon provided by the invention can well maintain good activity under medium and low temperature conditions.
According to fig. 5, the removal rate of the polyacid functionalized nitrogen-rich porous carbon prepared in example 4 is basically maintained at 100% within 1000min at 200 ℃, no obvious reduction occurs, and the polyacid functionalized nitrogen-rich porous carbon provided by the invention has excellent activity stability under medium and low temperature conditions.
From the above examples and comparative examples, the polyacid functionalized nitrogen-rich porous carbon provided by the invention has the best desulfurization effect, and the polyacid compound, the nitrogen-rich porous carbon, has poorer desulfurization effect and the nitrogen-rich porous carbon has the worst desulfurization effect. Compared with the method that the polyacid compound is simply taken as an active unit to directly introduce the polyacid compound into the nitrogen-rich porous carbon, the method takes the clathrate compound as the active unit to introduce the polyacid compound into the nitrogen-rich porous carbon, and the polyacid compound and the nitrogen-rich porous carbon can generate synergistic effect, so that the method not only realizes efficient selective removal, has excellent desulfurization effect, but also realizes the removal of hydrogen sulfide under the condition of medium and low temperature and normal pressure, keeps good activity, and realizes the recycling conversion of hydrogen sulfide into elemental sulfur.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (8)
1. A preparation method of polyacid functionalized nitrogen-rich porous carbon comprises the following steps:
(1) Mixing polyacid compounds, water and macrocyclic compounds for ultrasound to obtain inclusion compounds; the polyacid compound comprises one or more of polyoxometalate and polyoxometalate monomers;
(2) Mixing the inclusion compound, the nitrogen-containing compound, the activating agent and the carbon source for carbonization reaction to obtain polyacid functionalized nitrogen-rich porous carbon;
the macrocyclic compound is one or more of cyclodextrin, calixarene, crown ether, column arene and cucurbituril;
the polyoxometalate is one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid;
the polyoxometallate monomer is one or more of sodium tungstate, sodium molybdate and ammonium molybdate;
the temperature of the carbonization reaction is 300-1000 ℃ and the time is 0.5-10 h;
the mass ratio of the polyacid compound to the macrocyclic compound is 1:1.25;
the mass ratio of the polyacid compound to the water is 1: 1-100.
2. The method according to claim 1, wherein the mass ratio of the clathrate to the nitrogen-containing compound is 1: 1-100 parts;
the mass ratio of the inclusion compound to the activator is 1: 1-100 parts;
the mass ratio of the inclusion compound to the carbon source is 1: 1-180.
3. The production method according to claim 1, wherein the nitrogen-containing compound comprises one or more of an organic nitrogen-containing compound and an inorganic nitrogen-containing compound;
the activator comprises one or more of alkali metal bicarbonate and alkali metal hydroxide;
the carbon source is an organic carbon source.
4. The polyacid-functionalized nitrogen-rich porous carbon prepared by the preparation method of any one of claims 1-3.
5. The polyacid-functionalized nitrogen-rich porous carbon according to claim 4, wherein the nitrogen content of the nitrogen-rich porous carbon in the polyacid-functionalized nitrogen-rich porous carbon is 0.5% -10%; the specific surface area of the nitrogen-rich porous carbon is 100-2000 m 2 /g; the pore diameter of the nitrogen-rich porous carbon is 1-50 nm.
6. The application of the polyacid functionalized nitrogen-rich porous carbon in removal and conversion of hydrogen sulfide according to any one of claims 4-5.
7. The use according to claim 6, characterized by the steps of: and filling the polyacid functionalized nitrogen-rich porous carbon into a quartz tube, constructing a fixed bed reactor, introducing mixed gas to be treated, and removing hydrogen sulfide and converting into elemental sulfur.
8. The use according to claim 7, wherein the airspeed of the mixture is 3000-50000 mL/(g.h).
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