CN103432897A - Nitrogen-rich porous carbon desulfurizer and preparation method thereof - Google Patents
Nitrogen-rich porous carbon desulfurizer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-rich porous carbon desulfurizer and a preparation method thereof. The desulfurizer comprises a porous carbon material subjected to surface oxidation preprocessing and nitrogen-containing functional groups fixed to the surface of the porous carbon material by soaking and sintering, wherein the mass content of nitrogen element is 0.5-5.0% of the total mass of the nitrogen-rich porous carbon desulfurizer. The preparation method comprises the following steps: soaking the porous carbon material in a strong oxidant solution for surface oxidation preprocessing, mixing the strong oxidant solution with a nitrogen-containing compound solution, fully soaking, evaporating to remove the solvent, drying, putting the dried material into a high-temperature calcining furnace, calcining at the temperature of 400-1000 DEG C under the protection of inert gas, decomposing a nitrogen-containing compound, enabling the nitrogen-containing compound to react with the surface of active carbon, fully calcining, cooling to obtain the nitrogen-rich porous carbon desulfurizer. According to the nitrogen-rich porous carbon desulfurizer prepared by the preparation method, the content of the nitrogen functional groups on the surface of the carbon material is high and the desulfurization capacity is increased by 1.5-2 times in comparison with that of the active carbon desulfurizer which is directly subjected to surface nitrogen modification without surface oxidation preprocessing.
Description
Technical field
The present invention relates to the desulfurizing agent technology, be specifically related to a kind of porous carbon desulfurizing agent of enriching nitrogen-containing functional group and preparation method thereof that contains for the surface that removes industrial discharged waste gas sulfur dioxide, belong to Materials Science and Engineering, Chemical Engineering and field of environment protection.
Background technology
China SO
2pollute very serious, the annual SO to discharging in atmosphere
2surpass 2,000 ten thousand tons, occupy first place in the world.By SO
2the Acid Rain Pollution hazard area that discharge causes reaches 30% of area, has become the key factor of restriction China economy, social sustainable development.Therefore, strengthen SO
2the control dynamics of polluting is very urgent.
The Wet Flue Gas Desulfurization Technology that the lime stone-gypsum of take is representative is most widely used desulfur technology in current world wide.This method utilizes lime stone for absorbent, absorbs the SO in flue gas
2and generation accessory substance gypsum.Yet practical engineering application the time, this desulfur technology faces the problems such as equipment corrosion wearing and tearing are large, investment is large, accessory substance gypsum output is large, accessory substance gypsum value is not high.
It is desulfurizing agent that charcoal method flue gas desulfurization technique adopts the porous carbon materials such as granular activated carbon (GAC) or NACF (ACF), utilizes the nanoaperture structure of porous carbon materials by SO in flue gas
2absorption catalytic oxidation are SO
3, the desulfurizing agent adsorbed after saturated can be regenerated by the mode of washing or heating.Different from lime stone-gypsum desulfur technology by-product gypsum, the accessory substance of charcoal method flue gas desulfurization technique is dilute sulfuric acid (washing regeneration) or dense SO
2(thermal regeneration), value is high.
The porous carbon materials desulfurizing agent is the basis of charcoal method flue gas desulfurization technique, and the pore structure of its desulfurization performance and porous carbon materials (specific area, pore volume, aperture and pore-size distribution) and Surface Physical Chemistry characteristic (surface oxygen functional group and surperficial nitrogenous sense) relation is very large.Increase the quantity of the nitrogen-containing functional group of activated carbon surface, be conducive to improve that it is desulphurizing activated.Yet the porous carbon materials surface textures such as current merchandise active carbon are single, only contain very a small amount of oxygen-containing functional group, usually there is no nitrogen-containing functional group.When the porous carbon materials such as general goods activated carbon are carried out to flue gas desulfurization as desulfurizing agent, desulfurization performance is usually poor.
Prior art prepares nitrogenous porous carbon two class methods usually: 1) in raw materials for production, sneak into nitrogen-containing compound, the nitrogen element is embedded in carbon skeleton; 2) the finished product porous carbons such as active carbon, NACF are carried out to post processing, the surface by the nitrogen-containing functional group grafting at porous carbon.
Sneak into nitrogen-containing compound in the raw materials for production of the porous carbon materials such as active carbon, and, by processing such as carbonization, activation, can obtain nitrogenous active carbon.For example, in the patent document that is 200810035853.3 at the application number preparation method of disclosed a kind of nitrogenous pitch spherical activated charcoal.The method is sneaked into the nitrogen-containing compounds such as melamine or melamine resin in the raw materials such as the pitch of balling-up and naphthalene, then by balling-up, do not melt, prepare nitrogen-containing asphalt-base spherical activated after charing and activation process.The preparation method of disclosed a kind of rich nitrogen activated carbon electrodes in the patent document that is for example 201110291513.9 at application number again, the discarded wood-based plate that contains amine resin of the method utilization is raw material, prepare nitrogenous active carbon by carbonization, activating process, and be used as the electrode material of double layer capacitor.
According to the disclosed preparation method of application number 200810035853.3,201110291513.9 patent document, sneak into nitrogen-containing compound in raw material, and carry out carbonization and activation procedure processing with the raw material of producing active carbon simultaneously, can prepare nitrogenous active carbon.But, because activation procedure requires to carry out under the high temperature more than 900 ℃ usually, the pyrolytic of nitrogen-containing compound volatilization are more complete, therefore only have a small amount of nitrogen element to remain in active carbon.Simultaneously, the nitrogenous active carbon prepared according to these class methods, the nitrogen element is embedded in the skeleton of material with carbon element more equably, and the nitrogenous sense of activated carbon surface few.The desulfurization of active carbon or NACF is an adsorption and catalytic oxidation process, and the nitrogen element of body in mutually is little to the sweetening process contribution.Therefore, how to prepare the abundant rich nitrogen porous carbon desulfurizing agent of surperficial nitrogen-containing functional group still very important.
54 phases of volume of environmental project journal (2011) disclose that a kind of employing dipping high temperature Graft Method carries out the nitrogen modification to NACF and for flue gas desulfurization.In the document, activated carbon fiber is immersed in the aqueous solution of melamine, ammonium chloride, urea, heat-treats under nitrogen protection in chamber type electric resistance furnace after oven dry.NACF desulfurization performance after the nitrogen modification is improved.Yet, due to the carbonization structure on the surface of the material with carbon elements such as NACF, its surface hydrophobicity, reactivity are low, the more difficult grafting of nitrogen element is on the surface of the material with carbon elements such as NACF, and therefore, it is limited that the NACF desulfurization performance improves degree.
Summary of the invention
The problem existed for prior art, the present invention aims to provide a kind of surface and contains rich nitrogen porous carbon materials desulfurizing agent enriched nitrogen-containing functional group and preparation method thereof, the low problem of carbon material surface nitrogen-containing functional group content existed to overcome nitrogenous porous carbon materials desulfurizing agent prepared by prior art.
Basic conception of the present invention is: at first, the porous carbon materials such as the available active carbon of business, NACF are carried out to the surface oxidation pretreatment, increase the oxygen-containing functional group on porous carbon surface, improve its surface reaction activity; Then, will be immersed in the solution of the water of nitrogen-containing compound or organic solvent through pretreated porous carbon materials, and after the dipping certain hour, by the solvent evaporation, nitrogen-containing compound will be dispersed in the hole of porous carbon and on outer surface; Finally, in inert atmosphere, calcining is decomposed nitrogen-containing compound, and catabolite is at high temperature reacted with the surface carbon atom of porous carbon generates surperficial nitrogen-containing functional group, prepares rich nitrogen porous carbon desulfurizing agent.
Rich nitrogen porous carbon materials desulfurizing agent provided by the invention, by through the pretreated porous carbon materials of surface oxidation with anchor at the lip-deep nitrogen-containing functional group of porous carbon materials through impregnation sintering and form, wherein the mass content of nitrogen element is 0.5～5.0% of desulfurizing agent gross mass.Described porous carbon materials preferred particulates active carbon or NACF.
The method of the above-mentioned rich nitrogen porous carbon desulfurizing agent of preparation provided by the invention, comprise the steps:
(1) surface oxidation pretreatment: the available porous carbon materials of business is immersed in strong oxidant solution and carries out the surface oxidation pretreatment at not higher than the temperature of 60 ℃, increase the oxygen-containing functional group on porous carbon materials surface, fully after oxidation processes, take out, by deionized water rinsing to the pH value of cleaning solution, be 6～7, then drying enters subsequent processing after processing;
(2) nitrogen-containing compound dipping: nitrogen-containing compound is dissolved in solvent and is mixed with solution, with the porous carbon materials obtained through step (1) surface oxidation pretreatment, evenly mix, fully dipping is dispersed on the hole and outer surface of porous carbon materials nitrogen-containing compound, at not higher than the temperature of 100 ℃, the solvent in the porous carbon materials that is impregnated with nitrogen-containing compound is removed in evaporation, drying is processed and is entered subsequent processing again, and the mass ratio of porous carbon materials and nitrogen-containing compound is 1:0.02～3;
(3) high-temperature calcination: the porous carbon materials that is impregnated with nitrogen-containing compound that step (2) is obtained is put into the high-temperature calcination stove; be warming up to 400-1000 ℃ of calcining 0.5-12h under inert gas shielding; nitrogen-containing compound is decomposed and reacted with activated carbon surface, preparing surface after cooling contains the rich nitrogen porous carbon desulfurizing agent that enriches nitrogen-containing functional group.
In step (1), porous carbon materials used can be granular activated carbon, NACF etc., and source is restriction not.Active carbon can be the active carbon made of mineral raw material active carbon (as coal mass active carbon, asphalt based active carbon etc.), wood activated charcoal (as cocoanut active charcoal, apricot shell active carbon, wooden burgy etc.) or other raw material (active carbon of making as scrap rubber, waste plastics, agricultural residue etc.); NACF can be viscose-based active carbon fiber, asphalt based active carbon fiber or polypropylene cyano group NACF etc.Strong oxidizer used in step (1) can be selected nitric acid, phosphoric acid, or the mixed solution of sulfuric acid and potassium permanganate.The nitric acid that preferential selection mass concentration is 20-50%, preparation is comparatively economical.
The nitrogen-containing compound used in step (2) can be dicyanodiamine, urea, melamine, can be also any two or more mixture wherein.When using mixture, the ratio of each nitrogen-containing compound is restriction not.The nitrogen-containing compound solvent used such as dissolved urea can be the mixed liquor of water, ethanol, other organic solvent or water and organic solvent in step (2), if with mixed liquor during as solvent mixed proportion do not limit.The ratio that improves organic solvent can be accelerated the evaporation rate of solvent in drying steps.In step (2), the nitrogen-containing compound solution temperature is room temperature to 100 ℃, improves the use amount that solution temperature can reduce water or organic solvent.In step (2), the mass mixing ratio of the porous carbon materials such as nitrogen-containing compound and active carbon, NACF can be controlled in the scope of 1:0.02～3, and the nitrogen content of the rich nitrogen porous carbon desulfurizing agent prepared can be regulated by this mixed proportion.After in step (2), nitrogen-containing compound and porous carbon evenly flood, by the temperature of solvent evaporation, be room temperature to 100 ℃, preferentially be controlled at the scope of 40-100 ℃.Improve evaporating temperature and can save evaporation time, but be unfavorable for that nitrogen-containing compound mixes with the even of porous carbon.
Inert atmosphere in step (3) can be by passing into a certain amount of inert gas realization in the high-temperature calcination stove, and inert gas can be nitrogen, argon gas or helium.For reducing production costs, preferred nitrogen.Heating rate can be 1-20 ℃/min, under the prerequisite of ensuring the quality of products, saves time, preferably 3-10 ℃/min.Can be directly to rise to target temperature according to certain heating rate from room temperature, also can adopt to rise to after a certain temperature to keep the heating mode stage by stage heated up again after certain hour.
The rich nitrogen active carbon and the NACF desulfurizing agent that according to the present invention, prepare, the inventor removes SO in simulated flue gas to it in fixed bed reactors
2performance is tested.Test condition is: in simulated flue gas, content of sulfur dioxide is 0.3%, oxygen content is 10%, water vapour content is 8-20%, and bed temperature is 60-150 ℃, and air speed is 500-3000h
-1.In outlet, sulfur dioxide concentration is greater than 0.02%, finishes evaluation experimental and calculates desulfurization capacity.
The present invention has following technical characterstic and advantage:
(1) to take the available active carbon of business or NACF be raw material in the present invention, through the surface nitrogen doping vario-property, processes and prepare desulfurizing agent.Before carrying out the surface nitrogen doping vario-property, carry out oxidation pre-treatment by the surface to active carbon or NACF, improved the reactivity of the high-temperature decomposition product of carbon surface and nitrogen-containing compound.The rich nitrogen porous carbon desulfurizing agent surface nitrogen-containing functional group that adopts the present invention to prepare is abundant, and nitrogen content is between 0.5-5%.
(2) Desulfurizer that prepared by the present invention is good.With original activity charcoal or NACF, compare, its desulfurization capacity has improved 4-10 doubly; With carrying out the surface oxidation pretreatment, with regard to the active carbon or the NACF that directly carry out the surface nitrogen modification, do not compare, its desulfurization capacity has improved 1.5-2 doubly.
(3) the present invention utilizes the nitrogen-containing functional group on the porous carbon materials surfaces such as active carbon and NACF to carry out desulfurization for active component.At lower temperature, (<150 ℃) can be by SO in flue gas
2be catalytically conveted to SO
3, SO
3then react generation H with the steam in flue gas
2sO
4byproduct.With take the catalyst that the metal oxides such as Fe, Cu are active component and compare as desulfurizing agent, have the advantages that desulfuration efficiency is high.Simultaneously, because active component is not reacted with dilute sulfuric acid, thereby avoided the loss of active component fast, contained metal cation in the by-product dilute sulfuric acid and the problem such as the sour quality that causes is not high.
(4) the rich nitrogen porous carbon desulfurizing agent wide accommodation that prepared by the present invention.To SO in flue gas
2concentration is that 0.01%-0.8% has good desulfurized effect, outlet SO
2concentration can be lower than 100mg/Nm
3, SO
2the concentration wide accommodation; Simultaneously, being 30-150 ℃ in flue-gas temperature all has desulfurized effect preferably, and operating temperature accommodation is wide.
(5) the rich nitrogen porous carbon desulfurizing agent that prepared by the present invention, the active carbon that its mechanical strength is used in preparation process or the intensity of NACF determine.After the dipping nitrogen-containing compound, only need to carry out the high-temperature calcination processing, and not need to carry out further activation process, whole Process of Surface Modification can not cause the decline of the intensity of active carbon or NACF.
(6) the application number patent of invention such as be 200810035853.3, to prepare nitrogenous or rich nitrogen porous carbon by sneak into nitrogen substance in preparing the raw material of active carbon, with them, compare, the present invention directly adopts the available active carbon of business, NACF is raw material, just can prepare rich nitrogen porous carbon desulfurizing agent material by simple dipping and calcination processing, nitrogen-containing functional group in rich nitrogen porous carbon desulfurizing agent material is dispersed on the hole and outer surface of porous carbon materials, the nitrogen element can be utilized effectively, and preparation technology is simple, strong adaptability, application prospect is wide.
The accompanying drawing explanation
The specific embodiment
Below by the drawings and specific embodiments, the invention will be further described, and its purpose is better to understand content of the present invention but not to the restriction of content of the present invention.
NACF is immersed in the salpeter solution that mass concentration is 30%, and in 60 ℃ of waters bath with thermostatic control, stir process 2 hours is taken out, NACF with deionized water rinsing to pH=6-7, then in baking oven in 105 ℃ of dried overnight.100 gram dicyanodiamines are dissolved in the ethanol water that 200 milliliters of mass concentrations are 50%, are made into dicyanodiamine solution.NACF by 100 grams after pickling is poured in above-mentioned dicyanodiamine solution, while stir and heat under 60 ℃, slow evaporation falls ethanol and moisture, then in baking oven in 105 ℃ of dried overnight.By load the NACF of dicyanodiamine insert in the high-temperature calcination stove; under the condition of nitrogen protection; the heating rate of take rises to 750 ℃ as 5 ℃/min from room temperature; and under 750 ℃, keep 1 hour, obtain take the rich nitrogen NACF desulfurizing agent that dicyanodiamine is carried out the surface nitrogen doping as nitrogenous source after cooling.
Elementary analysis shows that its nitrogen element content is 4.1%, and as shown in Figure 1, its desulfurization capacity is 231mg/g to the desulfurization performance test result.
Comparative Examples 1
Original NACF is carried out to the desulfurization performance test, and as shown in Figure 1, it penetrates Sulfur capacity is 24.5mg/g to result.
Comparative Examples 2
100 gram dicyanodiamines are dissolved in the ethanol water of 200 milliliter 50%, are made into dicyanodiamine solution.100 gram NACFs were immersed in to above-mentioned dicyanodiamine solution after 24 hours, under 60 ℃ the heating, slow evaporation falls ethanol and moisture, then in baking oven in 105 ℃ of dried overnight.By load the active carbon of dicyanodiamine insert in the high-temperature calcination stove; under the condition of nitrogen protection; the heating rate of take rises to 750 ℃ as 5 ℃/min from room temperature; and under 750 ℃, keep 1 hour, obtain take the rich nitrogen NACF desulfurizing agent that dicyanodiamine is carried out the surface nitrogen doping as nitrogenous source after cooling.
Elementary analysis shows that its nitrogen element content is 3.1%, and as shown in Figure 1, its desulfurization capacity is 148mg/g to the desulfurization performance test result.
10-20 order granular activated carbon is immersed in the salpeter solution that mass concentration is 20%, stirs 3 hours in 60 ℃ of waters bath with thermostatic control.Granular activated carbon after pickling with deionized water rinsing to pH=6-7,105 ℃ of dried overnight in baking oven then.5 gram melamines are dissolved in 100 ml waters, are made into melamine solution.10-20 order granular activated carbon by 30 grams after pickling is poured in above-mentioned melamine solution, while stir and heat under 60 ℃, slow evaporation falls moisture, then 105 ℃ of dried overnight in baking oven.By load the granular activated carbon of melamine insert in the high-temperature calcination stove; under the condition of nitrogen protection; the heating rate of take rises to 800 ℃ as 5 ℃/min from room temperature; and under 800 ℃, keep 1 hour, obtain take the rich nitrogen granular activated carbon desulfurizing agent that melamine carries out the surface nitrogen doping as nitrogenous source after cooling.
Elementary analysis shows that its nitrogen element content is 3.5%, and as shown in Figure 2, it penetrates Sulfur capacity is 393mg/g to the desulfurization performance test result.
Comparative Examples 3
10-20 purpose primary granule active carbon is carried out to the desulfurization performance test, and as shown in Figure 2, it penetrates Sulfur capacity is 68mg/g to result.
Comparative Examples 4
5 gram melamines are dissolved in 100 ml waters, are made into melamine solution.30 gram 10-20 order granular activated carbons are poured in above-mentioned melamine solution, while stir and heat under 60 ℃, slow evaporation falls moisture, then 105 ℃ of dried overnight in baking oven.By load the active carbon of melamine insert in the high-temperature calcination stove; under the condition of nitrogen protection; the heating rate of take rises to 800 ℃ as 5 ℃/min from room temperature; and under 800 ℃, keep 1 hour, obtain take the rich nitrogen granular activated carbon desulfurizing agent that melamine carries out the surface nitrogen doping as nitrogenous source after cooling.
Elementary analysis shows that its nitrogen element content is 2.6%, and as shown in Figure 2, it penetrates Sulfur capacity is 255mg/g to the desulfurization performance test result.
10-20 order granular activated carbon is immersed in the salpeter solution that mass concentration is 50%, and under 60 ℃, reaction is 1 hour.Granular activated carbon after pickling with deionized water rinsing to pH=6-7,105 ℃ of dried overnight in baking oven then.200 gram urea are dissolved in the ethanol water that 1000 milliliters of mass concentrations are 50%, are made into urea liquid.Granular activated carbon by 100 grams after pickling is poured in above-mentioned urea liquid, while stir and heat under 60 ℃, slow evaporation falls ethanol and moisture, then 105 ℃ of dried overnight in baking oven.By load the active carbon of urea insert in the high-temperature calcination stove; under the condition of nitrogen protection; the heating rate of take rises to 850 ℃ as 5 ℃/min from room temperature, and under 850 ℃, keeps 1 hour, obtains take the rich nitrogen granular activated carbon desulfurizing agent that urea carries out the surface nitrogen doping as nitrogenous source after cooling.
Elementary analysis shows that its nitrogen element content is 3.7%, and as shown in Figure 3, its desulfurization capacity is 208mg/g to the desulfurization performance test result.
Comparative Examples 5
200 gram urea are dissolved in the ethanol water of 1000 milliliter 50%, are made into urea liquid.100 gram 10-20 order granular activated carbons are poured in above-mentioned urea liquid, while stir and heat under 60 ℃, slow evaporation falls ethanol and moisture, then 105 ℃ of dried overnight in baking oven.By load the active carbon of urea insert in the high-temperature calcination stove; under the condition of nitrogen protection; the heating rate of take rises to 750 ℃ as 5 ℃/min from room temperature, and under 750 ℃, keeps 1 hour, obtains take the rich nitrogen granular activated carbon desulfurizing agent that urea carries out the surface nitrogen doping as nitrogenous source after cooling.
Elementary analysis shows that its nitrogen element content is 3.1%, and as shown in Figure 3, its desulfurization capacity is 97mg/g to the desulfurization performance test result.
10-20 purpose granular activated carbon is immersed in the phosphoric acid solution that mass concentration is 30%, and under 60 ℃, reaction is 2 hours.Granular activated carbon after pickling with deionized water rinsing to pH=6-7,105 ℃ of dried overnight in baking oven then.100 gram urea are dissolved in 1000 ml waters, are made into urea liquid.10-20 order granular activated carbon by 100 grams after pickling is poured in above-mentioned urea liquid, while stir and heat under 60 ℃, slow evaporation falls moisture, then 105 ℃ of dried overnight in baking oven.By load the active carbon of urea insert in the high-temperature calcination stove, under the condition of nitrogen protection, the heating rate of take rises to 850 ℃ as 5 ℃/min from room temperature, and keeps 1 hour under 850 ℃, obtains rich nitrogen granular activated carbon desulfurizing agent after cooling.
10-20 order granular activated carbon is immersed in the concentrated sulfuric acid that 150 milliliters of mass concentrations are 98%, and ice bath slowly adds 18 gram potassium permanganate under stirring, and under ice bath, reaction is 1 hour, then under 35 ℃, reacts 1 hour.Granular activated carbon deionized water rinsing after surface oxidation treatment is to pH=6-7, then 105 ℃ of dried overnight in baking oven.100 gram urea are dissolved in 1000 ml waters, are made into urea liquid.10-20 order active carbon by 100 grams after surface oxidation treatment is poured in above-mentioned urea liquid, while stir and heat under 60 ℃, slow evaporation falls moisture, then 105 ℃ of dried overnight in baking oven.By load the active carbon of urea insert in the high-temperature calcination stove, under the condition of nitrogen protection, the heating rate of take rises to 800 ℃ as 5 ℃/min from room temperature, and keeps 1 hour under 800 ℃, obtains rich nitrogen granular activated carbon desulfurizing agent after cooling.
Claims (10)
1. a rich nitrogen porous carbon desulfurizing agent, it is characterized in that, by through the pretreated porous carbon materials of surface oxidation with anchor at the lip-deep nitrogen-containing functional group of porous carbon materials through impregnation sintering and form, wherein the mass content of nitrogen element is 0.5～5.0% of desulfurizing agent gross mass.
2. according to rich nitrogen porous carbon desulfurizing agent claimed in claim 1, it is characterized in that, described porous carbon materials is granular activated carbon or NACF.
3. prepare the method for the described rich nitrogen porous carbon desulfurizing agent of claim 1 or 2, comprise the steps:
(1) surface oxidation pretreatment: the available porous carbon materials of business is immersed in strong oxidant solution and carries out the surface oxidation pretreatment under not higher than 60 ℃, increase the oxygen-containing functional group on porous carbon materials surface, fully after oxidation processes, take out, by deionized water rinsing to the pH value of cleaning solution, be 6～7, then drying enters subsequent processing after processing;
(2) nitrogen-containing compound dipping: nitrogen-containing compound is dissolved in solvent and is mixed with solution, with the porous carbon materials obtained through step (1) oxidation pre-treatment, evenly mix, fully dipping is dispersed on the hole and outer surface of porous carbon materials nitrogen-containing compound, at not higher than the temperature of 100 ℃, the solvent in the porous carbon materials that is impregnated with nitrogen-containing compound is removed in evaporation, drying is processed and is entered subsequent processing again, and the mass ratio of porous carbon materials and nitrogen-containing compound is 1:0.02～3;
(3) high-temperature calcination: the porous carbon materials that is impregnated with nitrogen-containing compound that step (2) is obtained is put into the high-temperature calcination stove; be warming up to 400-1000 ℃ of calcining 0.5-12h under inert gas shielding; nitrogen-containing compound is decomposed and reacted with activated carbon surface, preparing surface after cooling contains the rich nitrogen porous carbon desulfurizing agent that enriches nitrogen-containing functional group.
4. according to rich nitrogen porous carbon desulfurizing agent preparation method claimed in claim 3, it is characterized in that, described strong oxidizer is selected from nitric acid, phosphoric acid, or the mixed solution of sulfuric acid and potassium permanganate.
5. according to rich nitrogen porous carbon desulfurizing agent preparation method claimed in claim 4, it is characterized in that, described strong oxidizer is selected the nitric acid that mass concentration is 20-50%.
6. according to rich nitrogen porous carbon desulfurizing agent preparation method claimed in claim 3, it is characterized in that, described nitrogen-containing compound is selected from dicyanodiamine, urea and melamine.
7. according to rich nitrogen porous carbon desulfurizing agent preparation method claimed in claim 3, it is characterized in that the mixed liquor that described solvent is water, ethanol, other organic solvent or water and organic solvent.
8. according to the described rich nitrogen porous carbon desulfurizing agent preparation method of one of claim 3 to 7, it is characterized in that, the described porous carbon materials that is impregnated with nitrogen-containing compound, in 40-100 ℃ of lower evaporative removal solvent, carries out drying in 105-150 ℃ and processes.
9. according to the described rich nitrogen porous carbon desulfurizing agent preparation method of one of claim 3 to 7, it is characterized in that, described calcining is warming up to 400～1000 ℃ according to 1-20 ℃/min heating rate.
10. according to rich nitrogen porous carbon desulfurizing agent preparation method claimed in claim 9, it is characterized in that, described calcining is warming up to 400～1000 ℃ according to 3-10 ℃/min heating rate.
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